Iodine promoted α- hydroxylation of ketones Supplementary Information Iodine promoted α-...

Electronic Supplementary Information

Iodine promoted α- hydroxylation of ketones

Yogesh Siddaraju and Kandikere Ramaiah Prabhu*

Department of Organic Chemistry

Indian Institute of Science

Bangalore 560 012, Karnataka, India

Fax: (+)91-80-23600529

*e-mail: [email protected]

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2015

mailto:[email protected]

Yogesh and Prabhu/Organic Chemistry/IISc

2

Contents

1. General experimental 3

2. Optimization table 4

3. Typical experimental procedures and characterization data for starting

material synthesis

5 – 15

4. Typical experimental procedure for α-hydroxylation of aryl ketones 16

5. Characterization data for α-hydroxy aryl ketones 17 – 31

6. References 32

7. 1H,

13C NMR Spectra of unknown starting materials 33 – 74

8. 1H,

13C NMR Spectra of products

72 – 155


3

General experimental

NMR spectra were recorded on a 400 MHz NMR spectrometers in CDCl3, tetramethylsilane (TMS; δ

= 0.00 ppm) served as an internal standard for 1H NMR. The corresponding residual non-deuterated

solvent signal (CDCl3; δ = 77.00 ppm) was used as internal standard for 13

C NMR. IR spectra were

measured using FT/IR spectrometers. Mass spectra were measured uisng Q-Tof (ESI-HRMS).

Column chromatography was carried out on Silica gel 100-200 mesh (commercial suppliers) and thin-

layer chromatography was carried out using SILICA GEL GF-254.


4

Table 1. Optimization studiesa

entry Catalyst (mol%) Oxidant (3 equiv) solvent conversionb

1 I2 (50) aq.TBHP DMSO 58%

2 I2 (50) aq.TBHP ACN NR

3 I2 (50) aq.TBHP DCE NR

4 I2 (50) aq.TBHP EtOAc NR

5 I2 (50) aq.TBHP toluene NR

6 I2 (50) aq.TBHP DMF NR

7 I2 (50) aq.TBHP DMA NR

8 KI (30) aq.TBHP DMSO NR

9 NaI (30) aq.TBHP DMSO NR

10 TBAI (30) aq.TBHP DMSO NR

11 TBAB (30) aq.TBHP DMSO NR

12 NIS (30) aq.TBHP DMSO NR

13 NCS (30) aq.TBHP DMSO NR

14 I2 (50) TBHP in decane DMSO 70%

15 I2 (50) O2 DMSO 41%

16 I2 (50) H2O2 DMSO 36%

17 I2 (50) oxone DMSO 18%

18 I2 (50) TBPB DMSO NR

19 I2 (50) m-CPBA DMSO NR

20 I2 (50) K2S2O8 DMSO NR

21 I2 (50) CHP DMSO NR



24 I2 (50) TBHP in decane DMSO 68% c

25 I2 (50) TBHP in decane DMSO 58% d

26 I2 (50) TBHP in decane DMSO NR e

27 I2 (50) TBHP in decane DMSO 60% f

28 I2 (50) ( None) Ar atmosphere DMSO 37% g

aReaction conditions: 1a (0.75 mmol), I2 (0.37 mmol), oxidant (2.24 mmol) in of DMSO (1 mL) at 80 °C.

bIsolated yield.

c4

Equiv of TBHP. d2 Equiv of TBHP.

e20 mol% of p-TSA was used.

f20 mol% piperidine was used.

g The reaction was performed

for 12h. DMA = N,N, Dimethyl acetamide. TBAI = tetra-n-butylammonium iodide, TBAB = tetra-n-butyl ammonium

bromide, NIS = N- iodosuccinimide, NCS = N-chlorosuccinimide, TBPB= tert-butyl peroxy benzoate, CHP = Cumene hydro

peroxide, NR = no reaction.


5

Experimental Section

Typical experimental procedure for Friedel Crafts acylation of arenes, starting material

synthesis

To a solution of anhydrous aluminium trichloride (1.1 equiv) in DCE (10 mL) at 0°C was added acid

chloride (1.1 equiv), slowly, the reaction mixture was stirred at 0 °C for 10 min, followed by addition

of a solution of arene in DCE (500 mg – 1g in 10 mL DCE, 1equiv) during 10 min, the reaction

mixture was slowly warmed to 50 °C and allowed to stir at 50 °C for completion of the reaction

(monitored by TLC), the reaction mixture was cooled to 0 °C and quenched with ice cold water (20

mL). The reaction mixture was extracted with ethyl acetate (3 x 20 mL), and combined organic layer

was washed with dilute HCl (25 mL, 2N), dilute sodium carbonate solution (25 mL, 5% aq solution)

and finally with water. The organic layer was dried over anhydrous Na2SO4 and concentrated under

reduced pressure. The crude product was purified on a silica gel column using hexane/EtOAc to get

the pure product.

1-Phenylbutan-1-one (1b).1 Yellow oily liquid; Yield 90%; Rf (hexane) 0.2. Prepared

as shown in the general experimental procedure (reaction completion time 2 h at 50

°C): 1H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 7.2 Hz, 2H), 7.55 (t, J = 7.2 Hz, 1H),

7.46 (t, J = 7.6 Hz, 2H), 2.95 (t, J = 7.2 Hz, 2H), 1.81 – 1.72 (m, 2H), 1.01 (t, J = 7.2

Hz, 3H).

1-Phenylpentan-1-one (1c).1 Yellow oily liquid; Yield 90%; Rf (hexane) 0.2.

Prepared as shown in the general experimental procedure (reaction completion time 2h

at 50 °C): 1H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 7.6 Hz, 2H), 7.55 (t, J = 7.2 Hz,

1H), 7.45 (t, J = 7.6 Hz, 2H), 2.97 (t, J = 7.2 Hz, 2H), 1.76 – 1.69 (m, 2H), 1.46 – 1.37

(m, 2H), 0.95 (t, J = 7.2 Hz, 3H).

6-methyl-1-phenylheptan-1-one (1d).2 Colorless oily liquid; Yield 76%; Rf

(hexane) 0.3. Prepared as shown in the general experimental procedure (reaction


6

completion time 2 h at 50 °C): 1H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 7.2 Hz, 2H), 7.55 (t, J = 7.2

Hz, 1H), 7.46 (t, J = 7.6 Hz, 2H), 2.97 (t, J = 7.2 Hz, 2H), 1.76 – 1.68 (m, 2H), 1.60 – 1.50 (m, 1H),

1.42 – 1.34 (m, 2H), 1.25 – 1.19 (m, 2H), 0.87 (d, J = 6.4 Hz, 6H).

1-Phenyldecan-1-one (1e).3

Colorless oily liquid; Yield 70%; Rf (hexane) 0.3.

Prepared as shown in thr general experimental procedure (reaction completion time

2 h at 50 °C): 1H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 7.2 Hz, 2H), 7.55 (t, J =

7.2 Hz, 1H), 7.45 (t, J = 7.6 Hz, 2H), 2.96 (t, J = 7.2 Hz, 2H), 1.77 – 1.70 (m, 2H),

1.34 – 1.27(m, 12H), 0.88 (t, J = 6.4 Hz, 3H).

1-(4-Ethylphenyl)butan-1-one (1f). Colourless oily liquid; Yield 92%; Rf (hexane) 0.3. Prepared as

shown in the general experimental procedure (reaction completion time 1 h at 50 °C): IR (Neat, cm−1

)

3348, 3032, 2965, 2933, 2874, 1682, 1606, 1568; 1H NMR (400 MHz, CDCl3) δ

7.89 (d, J = 8.0 Hz, 2H), 7.27 (d, J = 8.0 Hz, 2H), 2.92 (t, J = 7.2 Hz, 2H), 2.70 (q,

J = 7.6 Hz, 2H), 1.81 – 1.72 (m, 2H), 1.26 (t, J = 7.6 Hz, 3H), 1.00 (t, J = 7.2 Hz,

3H). 13

C NMR (100 MHz, CDCl3) δ 200.13, 149.74, 134.81, 128.24, 128.00,

40.41, 28.89, 17.85, 15.19, 13.89; HRESI-MS (m/z) Calculated for C12H16O (M+ + Na) 199.1099,

found (M+ + Na) 199.1094.

1-(4-(tert-butyl)phenyl)butan-1-one (1g).4 Colourless oily liquid; Yield 91%; Rf


completion time 1 h at 50 °C): 1H NMR (400 MHz, CDCl3) δ 7.91 (d, J = 8.4 Hz,

2H), 7.47 (d, J = 8.4 Hz, 2H), 2.92 (t, J = 7.2 Hz, 2H), 1.81 – 1.72 (m, 2H), 1.34

(s, 9H), 1.00 (t, J = 7.2 Hz, 3H).

1-(4-(tert-butyl)phenyl)pentan-1-one (1h).5

Colorless oily liquid; Yield 85%; Rf


completion time 1 h at 50 °C): 1H NMR (400 MHz, CDCl3) δ 7.91 (d, J = 8.0 Hz,

2H), 7.47 (d, J = 8.0 Hz, 2H), 2.94 (t, J = 7.2 Hz, 2H), 1.75 – 1.69 (m, 2H), 1.45 –

1.40 (m, 2H), 1.34 (s, 9H), 0.95 (t, J = 7.2 Hz, 3H).


7

1-(4-decylphenyl)butan-1-one (1i). Pale yellow oily liquid; Yield 88%; Rf (hexane) 0.4. Prepared as

shown in the general experimental procedure (reaction completion time 1 h at 50 °C): IR (Neat, cm−1

)

;3085, 3031, 2926, 2854, 1684, 1808, 1684, 1606, 1569; 1H NMR (400 MHz,

CDCl3) δ 7.88 (d, J = 8.4 Hz, 2H), 7.25 (d, J = 7.6 Hz, 2H), 2.92 (t, J = 7.2 Hz,

2H), 2.65 (t, J = 7.6 Hz, 2H), 1.81 – 1.71 (m, 2H), 1.66 – 1.58 (m, 2H), 1.31 –

1.25 (m, 14H), 1.00 (t, J = 7.2 Hz, 3H), 0.88 (t, J = 6.8 Hz, 3H); 13

C NMR (100

MHz, CDCl3) δ 200.11, 148.53, 134.80, 128.54, 128.16, 40.40, 35.95, 31.87,

31.11, 29.57, 29.53, 29.43, 29.30, 29.24, 22.66, 17.85, 14.09, 13.90; HRESI-MS (m/z) Calculated for

C20H32O (M+ + Na) 311.2351, found (M

+ + Na) 311.2353.

1-(4-benzylphenyl)pentan-1-one (1j). Pale yellow oily liquid; Yield 61%; Rf (5% EtOAc/hexane)

0.2. Prepared as shown in the general experimental procedure (reaction completion time 2 h at 50

°C): IR (Neat, cm−1

) 3582, 3346, 3059, 3027, 2957, 2867, 1681, 1603, 1569; 1H

NMR (400 MHz, CDCl3) δ 7.88 (d, J = 8.0 Hz, 2H), 7.30 – 7.20 (m, 5H), 7.17

(d, J = 7.6 Hz, 2H), 4.01 (s, 2H), 2.92 (t, J = 7.2 Hz, 2H), 1.74 – 1.66 (m, 2H),

1.44 – 1.34 (m, 2H), 0.94 (t, J = 7.2 Hz, 3H); 13

C NMR (100 MHz, CDCl3) δ

200.14, 146.45, 140.03, 135.10, 129.02, 128.88, 128.56, 128.38, 128.33, 126.33,


found (M+ + Na) 275.1411.

1-(5,6,7,8-tetrahydronaphthalen-2-yl)pentan-1-one (1k). Pale yellow oily liquid; Yield 62%; Rf

(5% EtOAc/hexane) 0.2. Prepared as shown in the general experimental procedure (reaction

completion time 2 h at 50 °C): IR (Neat, cm−1

) 3348, 3021, 2931, 2864, 2661, 1680,

1604, 1570; 1H NMR (400 MHz, CDCl3) δ 7.66 – 7.65 (m, 2H), 7.12 (d, J = 8.4 Hz,

1H), 2.92 (t, J = 7.2 Hz, 2H), 2.80 – 2.79 (m, 4H), 1.81 – 1.77 (m, 4H), 1.74 – 1.66

(m, 2H), 1.45 – 1.35 (m, 2H), 0.94 (t, J = 7.2 Hz, 3H); 13

C NMR (100 MHz, CDCl3)

δ 200.52, 142.80, 137.30, 134.55, 129.20, 128.89, 125.11, 38.16, 29.54, 29.33,


found (M+ + Na) 239.1416.


8

1-(9H-fluoren-2-yl)butan-1-one (1l). Pale yellow solid; mp: 120−122°C; Yield 53%; Rf (5%

EtOAc/hexane) 0.2. Prepared as shown in the general experimental procedure (reaction completion

time 3 h at 50 °C): IR (Neat, cm−1

) 3317, 3044, 2957, 2862, 2647, 1662,

1603, 1460; 1H NMR (400 MHz, CDCl3) δ 8.13 (s, 1H), 8.00 (d, J = 7.6

Hz, 1H), 7.83 – 7.80 (m, 2H), 7.56 (d, J = 7.2 Hz, 1H), 7.42 – 7.34 (m, 2H),

3.93 (s, 2H), 2.99 (t, J = 7.2 Hz, 2H), 1.85 – 1.75 (m, 2H), 1.03 (t, J = 7.2

Hz, 3H); 13

C NMR (100 MHz, CDCl3) δ 200.28, 146.15, 144.43, 143.24,

140.50, 135.52, 127.89, 127.37, 126.99, 125.20, 124.67, 120.79, 119.60, 40.63, 36.86, 17.95, 13.93;

HRESI-MS (m/z) Calculated for C17H16O (M+ + Na) 259.1099, found (M

+ + Na) 259.1094.

1-(5'-phenyl-[1,1':3',1''-terphenyl]-4-yl)butan-1-one (1m). White solid; Yield 52%; mp 109 −

111°C; Rf (5% EtOAc/hexane) 0.5. Prepared as shown in the general experimental procedure

(Reaction completion time 2 h at 50 °C): IR (KBr, cm−1

) 3337, 2959, 2931, 2868,

1674, 1597, 1495; 1H NMR (400 MHz, CDCl3) δ 8.05 (d, J = 8.0 Hz, 2H), 7.81 –

7.75 (m, 5H), 7.69 – 7.67 (m, 4H), 7.49 – 7.45 (m, 4H), 7.39 (t, J = 7.2 Hz, 2H),

2.97 (t, J = 7.2 Hz, 2H), 1.85 – 1.75 (m, 2H), 1.03 (t, J = 7.2 Hz, 3H); 13

C NMR

(100 MHz, CDCl3) δ 199.95, 145.37, 142.53, 140.80, 135.98, 128.87, 128.67,

127.67, 127.37, 127.30, 125.98, 125.12, 40.55, 17.80, 13.90; HRESI-MS (m/z) Calculated for

C28H24O (M+ + Na) 399.1725, found (M

+ + Na) 399.1728.

1-(4-benzhydrylphenyl)butan-1-one (1n). Pale yellow oily liquid; Yield 66%; Rf (5%

EtOAc/hexane) 0.5. Prepared as shown in the general experimental procedure (Reaction completion


) 3346, 3058, 3026, 2962, 2874, 1682,

1601, 1493, 1451; 1H NMR (400 MHz, CDCl3) δ 7.88 (d, J = 8.0 Hz, 2H),

7.29 – 7.27 (m, 4H), 7.22 – 7.18 (m, 4H), 7.09 (d, J = 7.2 Hz, 4H), 5.57 (s,

1H), 2.89 (t, J = 7.2 Hz, 2H), 1.79 – 1.69 (m, 2H), 0.98 (t, J = 7.2 Hz, 3H);

13C NMR (100 MHz, CDCl3) δ 199.89, 149.13, 142.94, 135.22, 129.54,

129.29, 128.38, 128.08, 126.52, 56.67, 40.36, 17.70, 13.83; HRESI-MS (m/z) Calculated for C23H22O

(M+ + Na) 337.1568, found (M

+ + Na) 337.1566.


9

1,1'-(5'-phenyl-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(butan-1-one) (3a). White solid; Yield 48%; mp

155 – 157; 122°C; Rf (5% EtOAc/hexane) 0.1. Prepared as shown in the general experimental

procedure (2.2 equiv of acid chloride and 2.2 equiv of aluminium

trichloride used) (reaction completion time 4 h at 50°C): IR (Neat,

cm−1

) 3330, 3040, 2956, 2498, 2044, 1977, 1917, 1673, 1594, 1495;

1H NMR (400 MHz, CDCl3) δ 8.07 (d, J = 8.0 Hz, 4H), 7.82 – 7.77

(m, 7H), 7.68 (d, J = 7.2 Hz, 2H), 7.49 (t, J = 7.2 Hz, 2H), 7.41 (t, J

= 7.2 Hz, 1H), 2.99 (t, J = 7.2 Hz, 4H), 1.85 – 1.76 (m, 4H), 1.03 (t, J

= 7.2 Hz, 6H). 13

C NMR (100 MHz, CDCl3) δ 199.88, 145.04, 142.74, 141.24, 140.49, 136.09,

128.92, 128.69, 127.82, 127.36, 127.27, 125.94, 125.10, 40.54, 17.76, 13.87. HRESI-MS (m/z)

Calculated for C32H30O2 (M+ + Na) 469.2143, found (M

+ + Na) 469.2148.

1,1'-((phenylmethylene)bis(4,1-phenylene))bis(butan-1-one) (3b). Pale yellow oily liquid; Yield

61%; Rf (10% EtOAc/hexane) 0.3. Prepared as shown in the general experimental procedure (2.2

equiv of acid chloride and 2.2 equiv of aluminium trichloride used)

(Reaction completion time 4 h at 50°C): IR (Neat, cm−1

) 3345, 3057,

3028, 2962, 2874, 1682, 1602, 1569; 1H NMR (400 MHz, CDCl3) δ

7.90 (d, J = 8.0 Hz, 4H), 7.32 – 7.19 (m, 7H), 7.09 (d, J = 7.2 Hz,

2H), 5.63 (s, 1H), 2.91 (t, J = 7.2 Hz, 4H), 1.78 – 1.70 (m, 4H), 0.99

(t, J = 7.2 Hz, 6H); 13

C NMR (100 MHz, CDCl3) δ 199.80, 148.18, 142.12, 135.46, 129.48, 129.21,

128.54, 128.20, 126.82, 56.57, 40.36, 17.66, 13.80; HRESI-MS (m/z) Calculated for C27H28O2 (M+ +

Na) 407.1987, found (M+ + Na) 407.1987.

1,9-diphenylnonane-1,9-dione (3c).6 Yellow solid; Yield 32 %; Rf (10%

EtOAc/hexane) 0.1. Prepared as shown in the general experimental procedure

(15 equiv of benzene, 1.1 equiv of acid chloride and 2.2 equiv of aluminium

trichloride used) (Reaction completion time 4 h at 50°C): 1H NMR (400 MHz,

CDCl3) δ 7.96 (d, J = 7.6 Hz, 4H), 7.55 (t, J = 7.2 Hz, 2H), 7.46 (t, J = 7.2 Hz,

4H), 2.96 (t, J = 7.2 Hz, 4H), 1.78 – 1.70 (m, 4H), 1.44 – 1.40 (m, 6H).


10

1,1'-(5'-(4-butyrylphenyl)-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(butan-1-one) (3d). White solid;

Yield 34%; mp 119 − 122°C; Rf (10% EtOAc/hexane) 0.1.

Prepared as shown in the general experimental procedure (3.3

equiv of acid chloride and 3.3 equiv of aluminium trichloride

used) (reaction completion time 4 h at 50°C): IR (KBr, cm−1

)

3339, 3185, 3054, 2959, 2930, 2871, 1673, 1596, 1562; 1H

NMR (400 MHz, CDCl3) δ 8.09 (d, J = 8.4 Hz, 6H), 7.86 (s,

3H), 7.78 (d, J = 8.0 Hz, 6H), 3.0 (t, J = 7.2 Hz, 6H), 1.86 –

1.76 (m, 6H), 1.04 (t, J = 7.2 Hz, 9H); 13

C NMR (100 MHz, CDCl3) δ 199.85, 144.76, 141.50,

136.23, 128.73, 127.39, 125.95, 40.56, 17.76, 13.86; HRESI-MS (m/z) Calculated for C36H36O3 (M+

+ Na) 539.2562, found (M+ + Na) 539.2566.

1-(4-phenoxyphenyl)pentan-1-one (5k). Colourless oily liquid; Yield 52%; Rf (5% EtOAc/hexane)

0.1. Prepared as shown in the general experimental procedure (reaction


) 3340, 3065, 2958, 2869, 2608,


7.39 (t, J = 7.6 Hz, 2H), 7.19 (t, J = 7.2 Hz, 1H), 7.07 (d, J = 8.0 Hz, 2H),

6.99 (d, J = 8.4 Hz, 2H), 2.92 (t, J = 7.2 Hz, 2H), 1.75 – 1.67 (m, 2H), 1.45 – 1.36 (m, 2H), 0.95 (t, J

= 7.2 Hz, 3H). 13

C NMR (100 MHz, CDCl3) δ 199.19, 161.73, 155.54, 131.78, 130.29, 130.01,

124.51, 120.10, 117.29, 38.11, 26.62, 22.49, 13.93. HRESI-MS (m/z) Calculated for C17H18O2 (M+ +

Na) 277.1204, found (M+ + Na) 277.1203.

1-(4-(phenylthio)phenyl)butan-1-one (5l). Pale yellow oily liquid; Yield 53%; Rf (5%

EtOAc/hexane) 0.1. Prepared as shown in the general experimental

procedure (reaction completion time 2 h at 50 °C): IR (Neat, cm−1

) 3221,

3060, 2962, 2873, 2561, 2132, 1680, 1586, 1474; 1H NMR (400 MHz,

CDCl3) δ 7.82 (d, J = 8.0 Hz, 2H), 7.49 – 7.48 (m, 2H), 7.39 – 7.38 (m, 3H),

7.21 (d, J = 8.0 Hz, 2H), 2.88 (t, J = 7.2 Hz, 2H), 1.79 – 1.69 (m, 2H), 0.98 (t, J = 7.2 Hz, 3H). 13

C

NMR (100 MHz, CDCl3) δ 199.40, 144.42, 134.40, 133.72, 132.18, 129.61, 128.67, 128.60, 127.52,


11

40.32, 17.77, 13.84; HRESI-MS (m/z) Calculated for C16H16OS (M+ + Na) 279.0820, found (M

+ +

Na) 279.0817.

1-(thiophen-2-yl)butan-1-one (7a).7

Dark brown oily liquid; Yield 84%; Rf


completion time 6 h at RT): 1H NMR (400 MHz, CDCl3) δ 7.71 (d, J = 3.6 Hz,

1H), 7.62 (d, J = 4.4 Hz, 1H), 7.12 (t, J = 4.0 Hz, 1H), 2.88 (t, J = 7.2 Hz, 2H), 1.83

– 1.74 (m, 2H), 1.00 (t, J = 7.2 Hz, 3H).

1-(5-methylthiophen-2-yl)butan-1-one (7b). Yellow oily liquid; Yield 83%; Rf (hexane) 0.2.

Prepared as shown in the general experimental procedure (reaction completion

time 6 h at RT): IR (Neat, cm−1

) 3300, 3073, 2963, 2930, 2873, 2737, 1658,

1455; 1H NMR (400 MHz, CDCl3) δ 7.52 (d, J = 3.6 Hz, 1H), 6.79 (d, J = 3.2

Hz, 1H), 2.81 (t, J = 7.2 Hz, 2H), 2.52 (s, 3H), 1.80 – 1.71 (m, 2H), 0.99 (t, J =

7.2 Hz, 3H). 13

C NMR (100 MHz, CDCl3) δ 193.07, 149.28, 142.27, 132.22, 126.58, 40.70, 18.30,

15.91, 13.79; HRESI-MS (m/z) Calculated for C9H12OS (M+ + Na) 191.0507, found (M

+ + Na)

191.0504.

1-(5-bromothiophen-2-yl)butan-1-one (7c). Dark brown oily liquid; Yield 70%; Rf (hexane) 0.2.


time 1 h at 50°C): IR (Neat, cm−1

) 3308, 3216, 3094, 2963, 2874, 2730, 2621,

1662, 1522, 1459; 1H NMR (400 MHz, CDCl3) δ 7.40 (d, J = 3.6 Hz, 1H), 7.09

(d, J = 3.6 Hz, 1H), 2.80 (t, J = 7.2 Hz, 2H), 1.80 – 1.71 (m, 2H), 0.99 (t, J =

7.2 Hz, 3H). 13

C NMR (100 MHz, CDCl3) δ 192.26, 145.91, 131.71, 131.11, 122.23, 40.52, 18.04,

13.76. HRESI-MS (m/z) Calculated for C8H9BrOS (M+ + Na) 254.9455, found (M

+ + Na) 254.9455.


12

Typical experimental procedure for friedel crafts acylation of arenes, indoles and furan

(starting material synthesis).

To a solution of anhydrous aluminium trichloride (1.1 equiv) in DCE (10 mL) at 0°C was added acid

chloride (1.1 equiv), slowly, the reaction mixture was stirred at 0 °C for 10 min, followed by addition

of a solution of arene in DCE (500 mg – 1g in 10 mL DCE, 1equiv) during 10 min, the reaction

mixture was slowly warmed to 50 °C and allowed to stir at 50 °C for completion of the reaction

(monitored by TLC), the reaction mixture was cooled to 0 °C and quenched with methanol (5 mL)

followed by water (30 mL). The reaction mixture was extracted with ethyl acetate (3 x 20 mL), and

combined organic layer was washed with dilute sodium carbonate solution (25 mL) and finally with

water. The organic layer was dried over anhydrous Na2SO4 and concentrated under reduced pressure.

The crude product was purified on a silica gel column using hexane/EtOAc to get the pure product.

1-(5-methylfuran-2-yl)butan-1-one (7d).8 Pale yellow oily liquid; Yield 25%; Rf (hexane) 0.3.


time 4 h at 50 °C): 1H NMR (400 MHz, CDCl3) δ 7.09 (d, J = 3.2 Hz, 1H), 6.14

(d, J = 3.2 Hz, 1H), 2.73 (t, J = 7.2 Hz, 2H), 2.39 (s, 3H), 1.79 – 1.70 (m, 2H),

0.98 (t, J = 7.2 Hz, 3H).

1-(1-methyl-1H-indol-3-yl)butan-1-one (7e). Yellow oily liquid; Yield 62%; Rf (10 %


(reaction completion time 2 h at 50 °C): IR (Neat, cm−1

) 3455, 3107, 3049,

2960, 2931, 2872, 2601, 1642, 1529, 1465; 1H NMR (400 MHz, CDCl3) δ 8.40

– 8.39 (m, 1H), 7.68 (s, 1H), 7.30 – 7.28 (m, 3H), 3.79 (s, 3H), 2.79 (t, J = 7.2

Hz, 2H), 1.84 – 1.75 (m, 2H), 1.01 (t, J = 7.2 Hz, 3H). 13

C NMR (101 MHz, CDCl3) δ 195.81,

137.34, 135.20, 126.23, 123.13, 122.49, 122.36, 116.49, 109.49, 41.75, 33.35, 18.58, 14.01. HRESI-

MS (m/z). Calculated for C13H15NO (M+ + Na) 224.1051, found (M

+ + Na) 224.1055.

1-(1-benzoyl-1H-indol-3-yl)butan-1-one (7f). White solid; Yield 56%; mp 106 − 108°C; Rf (5%


time 3 h at 50 °C): IR (KBr, cm−1

) 3382, 3307, 3138, 3057, 2960, 2927, 2523, 2321, 2209, 1917,


13

1739, 1697, 1663, 1599; 1H NMR (400 MHz, CDCl3) δ 8.41 – 8.38 (m, 1H),

8.24 – 8.21 (m, 1H), 7.93 (s, 1H), 7.79 – 7.77 (m, 2H), 7.67 (t, J = 7.6 Hz,

1H), 7.57 (t, J = 7.6 Hz, 2H), 7.41 – 7.38 (m, 2H), 2.76 (t, J = 7.2 Hz, 2H),

1.80 – 1.71 (m, 2H), 0.97 (t, J = 7.2 Hz, 3H). 13


196.41, 168.48, 136.37, 133.30, 132.74, 132.70, 129.35, 128.86, 127.55,

125.76, 125.16, 122.53, 121.00, 115.71, 41.79, 17.77, 13.76. HRESI-MS (m/z). Calculated for

C19H17NO2 (M+ + Na) 314.1157, found (M

+ + Na) 314.1157.

1-(1-benzoyl-5-methoxy-1H-indol-3-yl)butan-1-one (7g). White solid; Yield 61%; mp 128 − 130°C;

Rf (10% EtOAc/hexane) 0.1. Prepared as shown in the general

experimental procedure (reaction completion time 2 h at 50 °C): IR (KBr,

cm cm−1

) 3383, 3308, 3136, 3057, 3008, 2960, 2898, 2872, 2839, 2164,

1698, 1665, 1609; 1H NMR (400 MHz, CDCl3) δ 8.13 (d, J = 8.8 Hz,

1H), 7.91 (d, J = 2.4 Hz, 1H), 7.89 (s, 1H), 7.76 (d, J = 7.6 Hz, 2H), 7.68

(t, J = 7.2 Hz, 1H), 7.58 (t, J = 7.6 Hz, 2H), 7.01 (dd, J = 8.8, 2.4 Hz, 1H), 3.90 (s, 3H), 2.75 (t, J =

7.2 Hz, 2H), 1.81 – 1.72 (m, 2H), 0.98 (t, J = 7.6 Hz, 3H). 13

C NMR (100 MHz, CDCl3) δ 196.67,

168.30, 157.68, 133.34, 133.07, 132.68, 130.91, 129.34, 128.87, 128.70, 120.81, 116.60, 115.23,

104.27, 55.61, 41.64, 17.79, 13.81. HRESI-MS (m/z) Calculated for C20H19NO3 (M+ + Na)

344.1263, found (M+ + Na) 344.1268.

General procedure for O-benylation of 4- Hydroxy Propiophenone (starting material synthesis).

A mixture of 4-hydroxy propiophenone (500 mg, 1equiv), benzyl bromide (1.5equiv), potassium

carbonate (2 equiv) in acetonitrile (10 mL) was heated at reflux for 12h. After the completion of the

reaction (monitored by TLC), 50 mL water was added and the reaction mixture was extracted with

ethyl acetate (3x20 mL). The combined organic layer was washed with dilute sodium carbonate

solution (25 mL, 5% aqueous) and finally with water. The organic layer was dried over anhydrous

Na2SO4 and concentrated under reduced pressure. The crude product was purified on a silica gel

column using hexane/EtOAc to get the pure product.


14

1-(4-(benzyloxy)phenyl)propan-1-one (5f).9 White solid; Yield 81%; Rf (15% EtOAc/hexane) 0.3.

Prepared as shown in the general experimental procedure (reaction

completion time 12 h at 80°C): 1H NMR (400 MHz, CDCl3) δ 7.94

(d, J = 8.4 Hz, 2H), 7.43 – 7.32 (m, 5H), 7.00 (d, J = 8.4 Hz, 2H),

5.12 (s, 2H), 2.94 (q, J = 7.2 Hz, 2H), 1.21 (t, J = 7.2 Hz, 3H).

4'-((4-propionylphenoxy)methyl)-[1,1'-biphenyl]-2-carbonitrile (5g). White solid; Yield 68%; mp

118 − 120°C; Rf (20% EtOAc/hexane) 0.4. Prepared as

shown in the general experimental procedure (reaction

completion time 12 h at 80°C): IR (KBr, cm−1

) 3325,

3058, 2978, 2933, 2870, 2220, 2045, 1670, 1596, 1502,

1476; 1H NMR (400 MHz, CDCl3) δ 7.97 (d, J = 8.8 Hz,

2H), 7.77 (d, J = 7.6 Hz, 1H), 7.65 (t, J = 7.6 Hz, 1H), 7.61 – 7.50 (m, 5H), 7.45 (t, J = 7.6 Hz, 1H),

7.03 (d, J = 8.4 Hz, 2H), 5.19 (s, 2H), 2.96 (q, J = 7.2 Hz, 2H), 1.22 (t, J = 7.2 Hz, 3H). 13

C NMR

(100 MHz, CDCl3) δ 199.41, 162.24, 144.85, 136.79, 133.73, 132.85, 130.28, 130.22, 129.98, 129.04,

127.69, 118.61, 114.46, 111.17, 69.57, 31.38, 8.37. HRESI-MS (m/z) Calculated for C23H19NO2 (M+

+ Na) 364.1313, found (M+ + Na) 364.1314.

1-(4-((4-nitrobenzyl)oxy)phenyl)propan-1-one (5h). Yellow solid; Yield 72%; mp 119 − 122°C; Rf

(20% EtOAc/hexane) 0.4. Prepared as shown in the general

experimental procedure (reaction completion time 12 h at 80°C):

IR (KBr, cm−1

) 3508, 3321, 3043, 2936, 2724, 2445, 2320, 2167,

1670, 1596, 1506; 1H NMR (400 MHz, CDCl3) δ 8.26 (d, J = 8.4

Hz, 2H), 7.97 (d, J = 8.8 Hz, 2H), 7.62 (d, J = 8.4 Hz, 2H), 7.00

(d, J = 8.4 Hz, 2H), 5.24 (s, 2H), 2.96 (q, J = 7.2 Hz, 2H), 1.22 (t, J = 7.2 Hz, 3H). 13

C NMR (100

MHz, CDCl3) δ 199.35, 161.62, 147.68, 143.60, 130.72, 130.30, 127.60, 123.89, 114.43, 68.64, 31.45,

8.33. HRESI-MS (m/z) Calculated for C16H15NO4 (M+ + Na) 308.0899, found (M

+ + Na) 308.0898.


15

General procedure for O-benzoylation of 4- Hydroxy Propiophenone (starting material

synthesis).

To a solution of 4-hydroxy propiophenone (1equiv, 500 mg) and triethylammine (1.1equiv) in THF

(10 mL) at 0 °C was added benzoyl chloride (1.1equiv) drop wise for 10 min, and allowed reaction

mixture to stir at room temperature for 1 h. After the completion of the reaction (monitored by TLC),

50 mL of water was added and the reaction mixture was extracted with ethyl acetate (3x20 mL). The

combined organic layer was washed with dilute HCl (25 mL, 2N), followed by dilute sodium

carbonate solution (25 mL, 5% aqueous solution) and finally with water. The organic layer was dried

over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified on

a silica gel column using hexane/EtOAc to get the pure product.

4-propionylphenyl benzoate (5i). White solid; Yield 88%; mp 114 − 116°C; Rf (20% EtOAc/hexane)

0.6. Prepared as shown in the general experimental procedure. IR

(KBr, cm−1

) 3342, 3039, 2971, 2930, 2871, 2728, 1727, 1675, 1586;

1H NMR (400 MHz, CDCl3) δ 8.21 (d, J = 7.6 Hz, 2H), 8.06 (d, J =

8.4 Hz, 2H), 7.66 (t, J = 7.6 Hz, 1H), 7.53 (t, J = 7.6 Hz, 2H), 7.33

(d, J = 8.8 Hz, 2H), 3.02 (q, J = 7.2 Hz, 2H), 1.25 (t, J = 7.2 Hz, 3H); 13


199.56, 164.64, 154.47, 134.54, 133.88, 130.22, 129.63, 129.04, 128.65, 121.88, 31.78, 8.20; HRESI-

MS (m/z) Calculated for C16H14O3 (M+ + Na) 277.0841, found (M

+ + Na) 277.0841.

4-propionylphenyl 2-fluorobenzoate (5j). White solid; Yield 90%; mp 68 − 70°C; Rf (20%

EtOAc/hexane) 0.5. Prepared as shown in the general experimental

procedure. IR (KBr, cm−1

) 3345, 2978, 2935, 2874, 2522, 1738,

1678, 1595, 1486; 1H NMR (400 MHz, CDCl3) δ 8.12 – 8.02 (m,

3H), 7.65 – 7.57 (m, 1H), 7.35 – 7.15 (m, 4H), 3.02 (q, J = 7.2 Hz,

2H), 1.24 (t, J = 7.2 Hz, 3H). 13


199.63, 162.32 (d, J = 260 Hz),162.17 (d, J = 4 Hz), 154.06, 135.59, 135.50, 134.62, 132.70, 132.51,

129.62, 124.20 (d, J = 3.7 Hz), 121.82, 117.55 (d, J = 9 Hz), 117.26 (d, J = 22 Hz), 31.77, 8.17;

HRESI-MS (m/z) Calculated for C16H13O3F (M+ + Na) 295.0746, found (M

+ + Na) 295.0749.


16

Typical experimental procedure for α Hydroxylation of aryl ketones

Aryl ketones (100 mg, 0.75 mmol), molecular iodine (0.5 equiv. 0.37 mmol) and TBHP in decane

5.5M (3 equiv. 2.23 mmol) in DMSO (1 mL) were stirred at 80 °C (6-12 h) in a 5ml round bottomed

flask. After the completion of the reaction (monitored by TLC), added water (25 mL) and extracted

with ethylacetate (3x20mL). The combined organic layer was washed with dilute sodium thiosulphate

solution (10 mL, 5% aqueous solution) and water. The combined organic layer was dried over Na2SO4

and concentrated under reduced pressure. The crude product was purified on a silica gel column using

hexane/ EtOAc to get the pure product.

Typical experimental procedure for α-Hydroxylation of aryl di and tri ketones

Aryl ketones (100 mg, 0.75 mmol), molecular iodine (1 equiv. 0.75 mmol) and TBHP in decane 5.5M

(6 equiv. 4.47 mmol) in DMSO (2 mL) were stirred at 80 °C (6-12 h) in a 5ml round bottomed flask.

After the completion of the reaction (monitored by TLC), added water (25 mL) and extracted with

ethylacetate (3x20mL). The combined organic layer was washed with dilute sodium thiosulphate

solution (10 mL, 5% aqueous solution) and water. Organic layer was dried over Na2SO4 and

concentrated under reduced pressure. The crude product was purified on a silica gel column using

hexane/ EtOAc to get the pure product.


17

Characterization data

2-hydroxy-1-phenylpropan-1-one (2a):10

Yellow oily; Yield 70% (79 mg); Rf (10% EtOAc/hexane)

0.1. Prepared as shown in the general experimental procedure (reaction


) 3459, 3063, 2981, 2933, 1683,

1597, 1578; 1H NMR (400 MHz, CDCl3) δ 7.94 (d, J = 7.6 Hz, 2H), 7.63 (t, J

= 7.6 Hz, 1H), 7.51 (t, J = 7.6 Hz, 2H), 5.21 – 5.14 (m, 1H), 3.82 (d, J = 6.4

Hz, 1H), 1.45 (d, J = 6.8 Hz, 3H); 13

C NMR (100 MHz, CDCl3) δ 202.22,

133.83, 133.17, 128.71, 128.50, 69.17, 22.06; HRESI-MS (m/z) Calculated for C9H10O2 (M+ + Na)

173.0578, found (M+ + Na) 173.0578.

2-hydroxy-1-phenylbutan-1-one (2b):11

Yellow oily liquid; Yield 71% (87 mg); Rf (10%

EtOAc/hexane) 0.1. Prepared as shown in general experimental procedure (reaction completion time 6

h at 80 °C): IR (neat, cm−1

) 3789, 3700, 3472, 3062, 2967, 2931, 2877, 2360,

1677, 1597, 1579; 1H NMR (400 MHz, CDCl3) δ 7.92 (d, J = 7.2 Hz, 2H), 7.62 (t,

J = 7.2 Hz, 1H), 7.51 (t, J = 7.6 Hz, 2H), 5.08 – 5.06 (m, 1H), 2.01 – 1.91 (m,

1H), 1.67 – 1.57 (m, 1H), 0.94 (t, J = 7.2 Hz, 3H); 13



C10H12O2 (M+ + Na) 187.0735, found (M

+ + Na) 187.0733.

2-hydroxy-1-phenylpentan-1-one (2c):12



time 6 h at 80 °C): IR (neat, cm−1

) 3476, 3062, 2960, 2929, 2872, 2173, 1679,

1597, 1579, 1451; 1H NMR (400 MHz, CDCl3) δ 7.92 (d, J = 8.0 Hz, 2H), 7.62

(t, J = 7.6 Hz, 1H), 7.50 (t, J = 7.6 Hz, 2H), 5.09 (dd, J = 7.2, 3.6 Hz, 1H), 1.86 –

1.79 (m, 1H), 1.57 – 1.51 (m, 2H), 1.49 – 1.40 (m, 1H), 0.92 (t, J = 7.2 Hz, 3H);

13C NMR (100 MHz, CDCl3) δ 202.14, 133.84, 133.61, 128.79, 128.45, 72.87,


18

37.88, 18.17, 13.76; HRESI-MS (m/z) Calculated for C11H14O2 (M+ + Na) 201.0891, found (M

+ +

Na) 201.0892.

2-hydroxy-6-methyl-1-phenylheptan-1-one (2d): Colorless oily liquid; Yield 67% (111 mg); Rf (5%


time 6 h at 80 °C): IR (neat, cm−1

) 3019, 2954, 1748, 1679, 1401; 1H NMR

(400 MHz, CDCl3) δ 7.91 (d, J = 7.6 Hz, 2H), 7.62 (t, J = 7.2 Hz, 1H), 7.51

(t, J = 7.6 Hz, 2H), 5.10 – 5.06 (m, 1H), 3.72 (d, J = 6.4 Hz, 1H), 1.86 –

1.81 (m, 1H), 1.54 – 1.41 (m, 3H), 1.40 – 1.37 (m, 1H), 1.21 – 1.1 (m, 2H),

0.84 (dd, J = 6.4, 4.4 Hz, 6H); 13

C NMR (100 MHz, CDCl3) δ 202.18, 133.87, 133.68, 128.83,

128.48, 73.13, 38.56, 36.11, 27.83, 22.76, 22.59, 22.37; HRESI-MS (m/z) Calculated for C14H20O2

(M+ + Na) 243.1361, found (M

+ + Na) 243.1365.

2-hydroxy-1-phenyldecan-1-one (2e): Colorless oily liquid; Yield 63% (117 mg); Rf (5%



) 3788, 3699, 3472, 3055, 2925, 2854,

2324, 1726, 1678, 1597, 1449; 1H NMR (400 MHz, CDCl3) δ 7.91 (d, J = 7.2

Hz, 2H), 7.62 (t, J = 7.6 Hz, 1H), 7.51 (t, J = 7.6 Hz, 2H), 5.09 – 5.06 (m,

1H), 3.69 (d, J = 6.4 Hz, 1H), 1.90 – 1.81 (m, 1H), 1.6 – 1.47 (m, 2H), 1.39 –

1.37 (m, 1H), 1.31 – 1.23 (m, 10H), 0.86 (t, J = 6.4 Hz, 3H); 13

C NMR (100 MHz, CDCl3) δ 202.19,

133.87, 133.69, 128.83, 128.49, 73.11, 35.87, 31.78, 29.34, 29.32, 29.13, 24.88, 22.59, 14.05;

HRESI-MS (m/z) Calculated for C16H24O2 (M+ + Na) 271.1674, found (M

+ + Na) 271.1674.

1-(4-ethylphenyl)-2-hydroxybutan-1-one (2f): Colorless oily liquid; Yield 76% (109 mg); Rf (10%



) 3447, 2968, 2935, 2876, 2094, 1675,

1607, 1568; 1H NMR (400 MHz, CDCl3) δ 7.85 (d, J = 8.0 Hz, 2H), 7.32 (d,

J = 8.0 Hz, 2H), 5.04 (dd, J = 6.8, 4.0 Hz, 1H), 3.76 (s, 1H), 2.73 (q, J = 7.6

Hz, 2H), 2.01 – 1.91 (m, 1H), 1.67 – 1.56 (m, 1H), 1.27 (t, J = 7.6 Hz, 3H),


19

0.94 (t, J = 7.2 Hz, 3H); 13

C NMR (100 MHz, CDCl3) δ 201.58, 151.04, 131.28, 128.69, 128.30,

73.76, 28.97, 28.94, 15.03, 8.81; HRESI-MS (m/z) Calculated for C12H16O2 (M+ + Na) 215.1048,

found (M+ + Na) 215.1046.

1-(4-(tert-butyl)phenyl)-2-hydroxybutan-1-one (2g):13

Colorless oily liquid; Yield 71% (117 mg);

Rf (10% EtOAc/hexane) 0.3. Prepared as shown in the general experimental procedure (reaction


) 3474, 2963, 2872, 1736,

1674, 1604; 1H NMR (400 MHz, CDCl3) δ 7.86 (d, J = 8.4 Hz, 2H), 7.51

(d, J = 8.4 Hz, 2H), 5.05 (dd, J = 6.4, 3.6 Hz, 1H), 3.76 (s, 1H), 2.02 – 1.92

(m, 1H), 1.68 – 1.57 (m, 1H), 1.35 (s, 9H), 0.95 (t, J = 7.6 Hz, 3H); 13

C

NMR (100 MHz, CDCl3) δ 201.52, 157.76, 130.97, 128.43, 125.74, 73.76,

35.16, 30.95, 28.90, 8.83; HRESI-MS (m/z) Calculated for C14H20O2 (M+ + Na) 243.1361, found (M

+

+ Na) 243.1360.

1-(4-(tert-butyl)phenyl)-2-hydroxypentan-1-one (2h): Colorless oily liquid; Yield 67% (118 mg);



) 3714, 3477, 2961, 2870,

1950, 1676, 1604, 1563, 1463; 1H NMR (400 MHz, CDCl3) δ 7.86 (d, J =

8.4 Hz, 2H), 7.51 (d, J = 8.4 Hz, 2H), 5.07 (dd, J = 7.2, 3.2 Hz, 1H), 1.89 –

1.81 (m, 1H), 1.58 – 1.50 (m, 2H), 1.48 – 1.43 (m, 1H), 1.35 (s, 9H), 0.93

(t, J = 7.6 Hz, 3H); 13

C NMR (100 MHz, CDCl3) δ 201.67, 157.80, 130.92,


(M+ + Na) 257.1517, found (M+ + Na) 257.1513.

1-(4-decylphenyl)-2-hydroxybutan-1-one (2i): Colorless oily liquid; Yield 73% (167 mg); Rf (5%

EtOAc/Hexane) 0.2. Prepared as shown in the general experimental procedure (reaction completion


) 3475, 2923, 2853, 2359, 1675, 1606,

1567; 1H NMR (400 MHz, CDCl3) δ 7.84 (d, J = 8.0 Hz, 2H), 7.30 (d, J

= 8.0 Hz, 2H), 5.04 (dd, J = 6.8, 4.0 Hz, 1H), 2.67 (t, J = 7.6 Hz, 3H),


20

2.01 – 1.91 (m, 1H), 1.67 – 1.58 (m, 3H), 1.31 – 1.25 (m, 14H), 0.94 (t, J = 7.2 Hz, 3H), 0.88 (t, J =

6.8 Hz, 3H); 13

C NMR (100 MHz, CDCl3) δ 201.57, 149.88, 131.24, 128.84, 128.62, 73.76, 36.06,

31.85, 31.01, 29.56, 29.51, 29.41, 29.28, 29.24, 28.97, 22.64, 14.08, 8.85; HRESI-MS (m/z)


+ + Na) 327.2300.

1-(4-benzylphenyl)-2-hydroxypentan-1-one (2j): Yellow oily liquid; Yield 62% (124 mg); Rf (10%



) 3473, 3027, 2958, 2928, 2870, 1948,


7.32 – 7.30 (m, 4H), 7.26 – 7.22 (m, 1H), 7.19 (d, J = 7.2 Hz, 2H), 5.05 –

5.03 (m, 1H), 4.05 (s, 2H), 3.69 (s, 1H), 1.84 – 1.79 (m, 1H), 1.57 – 1.48

(m, 2H), 1.46 – 1.39 (m, 1H), 0.91 (t, J = 7.2 Hz, 3H); 13

C NMR (100

MHz, CDCl3) δ 201.67, 147.82, 139.66, 131.61, 129.32, 128.97, 128.83, 128.67, 126.52, 72.81, 41.95,

38.07, 18.24, 13.80; HRESI-MS (m/z) Calculated for C18H20O2 (M+ + Na) 291.1361, found (M

+ +

Na) 291.1361.

2-hydroxy-1-(5,6,7,8-tetrahydronaphthalen-2-yl)pentan-1-one (2k): Yellow oily liquid; Yield 61%

(106 mg); Rf (10% EtOAc/hexane) 0.1. Prepared as shown in the general experimental procedure


) 3328, 2943, 2830,

2497, 2056, 1676, 1450; 1H NMR (400 MHz, CDCl3) δ 7.63 (s, 1H), 7.60 (d, J

= 8.4 Hz, 1H), 7.17 (d, J = 8.0 Hz, 1H), 5.06 – 5.03 (m, 1H), 3.74 (s, 1H), 2.84

– 2.82 (m, 4H), 1.84 – 1.79 (m, 5H), 1.57 – 148 (m, 2H), 1.44 – 1.38 (m,

1H), 0.92 (t, J = 6.8 Hz, 3H); 13

C NMR (100 MHz, CDCl3) δ 201.95, 144.24,

137.83, 131.02, 129.50, 129.35, 125.50, 72.69, 38.14, 29.67, 29.31, 22.79, 22.66, 18.14, 13.82;

HRESI-MS (m/z) Calculated for C15H20O2 (M+ + Na) 255.1361, found (M

+ + Na) 255.1361.


21

1-(9H-fluoren-2-yl)-2-hydroxybutan-1-one (2l): Dark Yellow solid; (mp. 86-88°C) Yield 60% (114

mg); Rf (10% EtOAc/hexane) 0.1. Prepared as shown in the general experimental procedure (reaction


) 3765, 3455, 3056, 2966,

2932, 2876, 2332, 2079, 1667, 1608; 1H NMR (400 MHz, CDCl3) δ 8.09

(s, 1H), 7.94 (d, J = 8.0 Hz, 1H), 7.83 (d, J = 7.6 Hz, 2H), 7.58 (d, J = 6.8

Hz, 1H), 7.43 – 7.37 (m, 2H), 5.11 (dd, J = 6.0, 4.0 Hz, 1H), 3.94 (s, 2H),

3.83 (s, 1H), 2.05 – 1.95 (m, 1H), 1.72 – 1.61 (m, 1H), 0.97 (t, J = 7.2 Hz,

3H); 13

C NMR (100 MHz, CDCl3) δ 201.69, 147.27, 144.44, 143.44, 140.13, 131.84, 128.30, 127.81,

127.09, 125.23, 125.07, 120.94, 119.83, 73.86, 36.81, 29.04, 8.86; HRESI-MS (m/z) Calculated for

C17H16O2 (M+ + Na) 275.1048, found (M

+ + Na) 275.1048.

2-hydroxy-1-(5'-phenyl-[1,1':3',1''-terphenyl]-4-yl)butan-1-one (2m): Colorless oily liquid; Yield

63% (184 mg); Rf (10% EtOAc/hexane) 0.2. Prepared as shown in the general experimental procedure


) 3700,

3471, 3057, 3035, 2964, 2927, 2874, 2360, 1952, 1805, 1673, 1598,

1496; 1H NMR (400 MHz, CDCl3) δ 8.03 (d, J = 8.0 Hz, 2H), 7.85

– 7.80 (m, 5H), 7.70 (d, J = 7.2 Hz, 4H), 7.50 (t, J = 7.2 Hz, 4H),

7.41 (t, J = 7.2 Hz, 2H), 5.11 (dd, J = 6.8, 4.0 Hz, 1H), 3.75 (s, 1H),

2.07 – 1.97 (m, 1H), 1.71 – 1.60 (m, 1H), 0.98 (t, J = 7.2 Hz, 3H);

13C NMR (100 MHz, CDCl3) δ 201.60, 146.58, 142.65, 140.71,

132.55, 129.15, 128.92, 127.76, 127.69, 127.31, 126.28, 125.16, 73.97, 28.93, 8.88; HRESI-MS

(m/z) Calculated for C28H24O2 (M+ + Na) 415.1674, found (M

+ + Na) 415.1675.

1-(4-benzhydrylphenyl)-2-hydroxybutan-1-one (2n): Yellow oily liquid;

Yield 63% (156 mg); Rf (10% EtOAc/hexane) 0.3. Prepared as shown in

the general experimental procedure (reaction completion time 6 h at 80

°C): IR (Neat, cm−1

) 3478, 3027, 2922, 2852, 1736, 1676, 1598; 1H NMR

(400 MHz, CDCl3) δ 7.84 (d, J = 8.0 Hz, 2H), 7.32 – 7.21 (m, 8H), 7.10


22

(d, J = 7.6 Hz, 4H), 5.60 (s, 1H), 5.01 (dd, J = 6.8, 3.6 Hz, 1H), 3.70 (s, 1H), 1.99 – 1.89 (m, 1H),

1.65 – 1.55 (m, 1H), 0.94 (t, J = 7.2 Hz, 3H); 13

C NMR (100 MHz, CDCl3) δ 201.55, 150.50, 142.70,

131.77, 129.87, 129.33, 128.59, 128.50, 126.70, 73.86, 56.81, 28.89, 8.91; HRESI-MS (m/z)


+ + Na) 353.1519.

2-hydroxy-1,3-diphenylpropan-1-one (2o):14

Pale yellow solid (mp. 62-65°C); Yield 50% (85 mg);



) 3466, 3062, 3029, 2925,

2359, 1682, 1597, 1495; 1H NMR (400 MHz, CDCl3) δ 7.92 (d, J = 7.2 Hz,

2H), 7.63 (t, J = 7.2 Hz, 1H), 7.51 (t, J = 7.6 Hz, 2H), 7.26 – 7.20 (m, 3H),

7.12 (d, J = 6.8 Hz, 2H), 5.34 – 5.31 (m, 1H), 3.72 (s, 1H), 3.19 (dd, J =

14.0, 4.0 Hz, 1H), 2.89 (dd, J = 14.4, 7.2 Hz, 1H); 13

C NMR (100 MHz, CDCl3) δ 200.97, 136.42,

133.96, 133.80, 129.39, 128.90, 128.56, 128.27, 126.76, 73.69, 41.87; HRESI-MS (m/z) Calculated

for C15H14O2 (M+ + Na) 249.0891, found (M

+ + Na) 249.0892.

2-hydroxy-1-(3-(trifluoromethyl)phenyl)propan-1-one (2p): Yellow oily liquid; Yield 59% (97

mg); Rf (10% EtOAc/hexane) 0.1. Prepared as shown in the general experimental procedure (reaction


) 3427, 2925, 2854, 1692, 1612; 1H

NMR (400 MHz, CDCl3) δ 8.20 (s, 1H), 8.11 (d, J = 7.6 Hz, 1H), 7.89 (d, J =

7.6 Hz, 1H), 7.68 (t, J = 7.6 Hz, 1H), 5.20 (q, J = 6.8 Hz, 1H), 3.7 (s, 1H), 1.48

(d, J = 6.8 Hz, 3H). 13

C NMR (100 MHz, CDCl3) δ 201.170, 134.03, 131.61 (q,

2JC-F = 31.6 Hz), 131.70 – 131.69 (m), 130.27 (q,

3JC-F = 3.6 Hz), 129.54, 125.44 (q,

3JC-F = 3.7 Hz),

123.45 (q, 1JC-F = 271 Hz), 69.52, 21.91;

19F NMR (100 MHz, CDCl3) δ -62.96; HRESI-MS (m/z)

Calculated for C10H9F3O2 (M+ + Na) 241.0452, found (M

+ + Na) 241.0449.

1,1'-(5'-phenyl-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(2-hydroxybutan-1-one) (4a): Pale yellow oily

liquid; Yield 45% (161 mg); Rf (20% EtOAc/hexane) 0.1. Prepared as shown in the general

experimental procedure (reaction completion time 8 h at 80 °C): IR (Neat, cm−1

) 3480, 2966, 1675,

1603, 1559, 1457; 1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 8.4 Hz, 4H), 7.87 – 7.81 (m, 7H), 7.70


23

(d, J = 7.6 Hz, 2H), 7.51 (t, J = 7.2 Hz, 2H), 7.45 – 7.42 (m, 1H), 5.11

(dd, J = 6.4, 3.6 Hz, 2H), 3.72 (s, 2H), 2.05 – 1.98 (m, 2H), 1.72 – 1.64

(m, 2H), 0.99 (t, J = 7.2 Hz, 6H); 13


201.58, 146.14, 143.01, 141.08, 140.34, 132.79, 129.21, 129.01, 128.00,

127.71, 127.29, 126.28, 125.18, 74.00, 28.91, 8.87; HRESI-MS (m/z)


+ + Na)

501.2036.

1,1'-((phenylmethylene)bis(4,1-phenylene))bis(2-hydroxybutan-1-one) (4b): Pale yellow oily

liquid; Yield 47% (147 mg); Rf (20% EtOAc/hexane) 0.2. Prepared as shown in the general

experimental procedure (reaction completion time 8 h at 80 °C): IR

(Neat, cm−1

) 3855, 3395, 2918, 2851, 2364, 2345, 1676, 1420; 1H NMR

(400 MHz, CDCl3) δ 7.87 (d, J = 8.0 Hz, 4H), 7.36 – 7.28 (m, 3H), 7.25

(d, J = 8.0 Hz, 4H), 7.09 (d, J = 7.6 Hz, 2H), 5.66 (s, 1H), 5.02 (dd, J =

6.4, 3.6 Hz, 2H), 3.68 (s, 2H), 2.0 – 1.90 (m, 2H), 1.66 – 1.55 (m, 2H),

0.95 (t, J = 7.2 Hz, 6H); 13

C NMR (100 MHz, CDCl3) δ 201.48, 149.20,

141.61, 132.17, 129.82, 129.26, 128.78, 128.76, 127.16, 73.92, 56.79, 28.86, 8.91; HRESI-MS (m/z)


+ + Na) 439.1884.

2-hydroxy-1,9-diphenylnonane-1,9-dione (4ca): Pale yellow oily liquid; Yield 42 % (102 mg); Rf


completion time 5.5 h at 80 °C): IR (Neat, cm−1

) 3474, 3062, 3020, 2928,

2855, 1677, 1597, 1449; 1H NMR (400 MHz, CDCl3) δ 7.99 – 7.90 (m, 4H),

7.62 (t, J = 7.2 Hz, 1H), 7.57 – 7.43 (m, 5H), 5.08 (dd, J = 6.8, 3.2 Hz, 1H),

3.68 (s, 1H), 2.93 (t, J = 7.2 Hz, 2H), 1.90 – 1.84 (m, 1H), 1.72 – 1.68 (m,

2H), 1.56 – 1.49 (m, 2H), 1.36 – 1.25 (m, 5H); 13


202.07, 200.38, 136.94, 133.89, 133.58, 132.84, 128.83, 128.49, 128.46,


(M+ + Na) 347.1623, found (M

+ + Na) 347.1623.


24

2,8-dihydroxy-1,9-diphenylnonane-1,9-dione (4cb): Pale yellow oily liquid; Yield 25% (64 mg); Rf


completion time 5.5 h at 80 °C): IR (Neat, cm−1

) 3470, 2927, 2856, 1679,


7.62 (t, J = 7.6 Hz, 2H), 7.50 (t, J = 7.6 Hz, 4H), 5.06 – 5.02 (m, 2H), 3.67 (s,

2H), 1.86 – 1.80 (m, 2H), 1.55 – 1.45 (m, 4H), 1.42 – 1.23 (m, 4H); 13

C

NMR (100 MHz, CDCl3) δ 202.02, 133.93, 133.56, 128.85, 128.46, 72.97,

72.90, 35.70, 35.59, 29.03, 28.88, 24.75, 24.58; HRESI-MS (m/z)


+ + Na) 363.1569.

1,1'-(5'-(4-(2-hydroxybutanoyl)phenyl)-[1,1':3',1''-terphenyl]-4,4''-diyl)bis(butan-1-one) (4d):

Yellow oily liquid: Yield 25% (99 mg); Rf (20% EtOAc/hexane) 0.5. Prepared as shown in the general

experimental procedure (reaction completion time 5 h at 80 °C): IR (Neat, cm−1

) 3722, 3482, 3018,

2927, 2360, 1676, 1599, 1212; 1H NMR (400 MHz, CDCl3) δ

8.10 (d, J = 8.4 Hz, 4H), 8.06 (d, J = 8.0 Hz, 2H), 7.88 (s, 1H),

7.81 (s, 2H), 7.83 (d, J = 8.0 Hz, 2H), 7.79 (d, J = 8.4 Hz,

4H), 5.14 – 5.10 (m, 1H), 3.74 (d, J = 6.4 Hz, 1H), 3.01 (t, J =

7.2 Hz, 4H), 2.05 – 1.99 (m, 1H), 1.86 – 1.77 (m, 4H), 1.72 –

1.66 (m, 1H), 1.04 (t, J = 7.6 Hz, 6H), 0.99 (t, J = 7.2 Hz, 3H);

13C NMR (100 MHz, CDCl3) δ 201.59, 199.94, 145.99,

144.72, 141.69, 141.26, 136.35, 132.89, 129.24, 128.81, 127.75, 127.45, 126.30, 126.03, 74.02, 40.63,


+

+ Na) 555.2514.

1-(4-bromophenyl)-2-hydroxypropan-1-one (6a):15

Yellow oily liquid;

Yield 70% (120 mg); Rf (10% EtOAc/hexane) 0.2. Prepared as shown in the

general experimental procedure (reaction completion time 8 h at 80 °C): IR

(Neat, cm−1

) 3454, 3090, 2932, 2981, 1686, 1586, 1567; 1H NMR (400 MHz,

CDCl3) δ 7.80 (d, J = 8.4 Hz, 2H), 7.65 (d, J = 8.4 Hz, 2H), 5.12 (q, J = 6.8 Hz, 1H), 3.73 (s, 1H),


25

1.44 (d, J = 7.2 Hz, 3H); 13

C NMR (100 MHz, CDCl3) δ 201.37, 132.20, 132.00, 130.04, 129.21,

69.26, 22.12; HRESI-MS (m/z) Calculated for C9H9BrO2 (M+ + Na) 250.9684, found (M

+ + Na)

250.9689.

1-(3-bromophenyl)-2-hydroxypropan-1-one (6b):16

Yellow oily liquid; Yield 70% (119 mg); Rf



) 3437, 3065, 2982, 2932, 1727,

1688, 1556; 1H NMR (400 MHz, CDCl3) δ 8.07 (s, 1H), 7.84 (d, J = 8.0 Hz,

1H), 7.75 (d, J = 7.6 Hz, 1H), 7.39 (t, J = 8.0Hz, 1H), 5.12 (q, J = 7.2 Hz, 1H),

3.71 (s, 1H), 1.45 (d, J = 7.2 Hz, 3H); 13

C NMR (100 MHz, CDCl3) δ 201.14,


C9H9BrO2 (M+ + Na) 250.9684, found (M

+ + Na) 250.9680.

1-(4-chlorophenyl)-2-hydroxypropan-1-one (6c):17




) 3457, 3071, 2982,

2933, 1686, 1591, 1570; 1H NMR (400 MHz, CDCl3) δ 7.88 (d, J = 8.4 Hz,

2H), 7.49 (d, J = 8.4 Hz, 2H), 5.12 (q, J = 7.2 Hz, 1H), 1.45 (d, J = 7.2 Hz,

3H); 13

C NMR (100 MHz, CDCl3) δ 201.16, 140.45, 131.59, 129.98, 129.20,

69.26, 22.13; HRESI-MS (m/z) Calculated for C9H9ClO2 (M+ + Na) 207.0189, found (M

+ + Na))

207.0185.

1-(3-chlorophenyl)-2-hydroxypropan-1-one (6d):18

Colorless oily liquid; Yield 68% (94 mg); Rf



) 3454, 3070, 2983, 2933, 1690,

1572; 1H NMR (400 MHz, CDCl3) δ 7.91 (s, 1H), 7.80 (d, J = 7.6 Hz, 1H),

7.60 (d, J = 7.6 Hz, 1H), 7.46 (t, J = 8.0 Hz, 1H), 5.12 (q, J = 6.8 Hz, 1H),

1.45 (d, J = 6.8 Hz, 3H); 13

C NMR (100 MHz, CDCl3) δ 201.23, 135.22,

134.90, 133.84, 130.16, 128.62, 126.63, 69.45, 22.04; HRESI-MS (m/z)


26

Calculated for C9H9ClO2 (M+ + Na) 207.0189, found (M

+ + Na) 207.0190.

1-(3-fluorophenyl)-2-hydroxypropan-1-one (6e):16




) 3436, 3075, 2983, 2934, 1693, 1588; 1H

NMR (400 MHz, CDCl3) δ 7.71 (d, J = 7.6 Hz, 1H), 7.63 (d, J = 9.2 Hz, 1H),

7.50 (dd, J = 13.6, 7.6 Hz, 1H), 7.35 – 7.31 (m, 1H), 5.13 (q, J = 6.8 Hz, 1H),

3.68 (s 1H), 1.46 (d, J = 6.8 Hz, 3H); 13

C NMR (100 MHz, CDCl3) δ 201.24,

162.80 (d, J = 247 Hz), 135.36 (d, J = 6 Hz), 130.58 (d, J = 8 Hz), 124.33 (d, J

= 3 Hz), 121.00 (d, J = 21 Hz), 115.39 (d, J = 22 Hz), 69.50, 22.08. HRESI-MS (m/z) Calculated for

C9H9FO2 (M+ + Na) 191.0484, found (M

+ + Na) 191.0480.

1-(4-(benzyloxy)phenyl)-2-hydroxypropan-1-one (6f): Yellow solid; (mp. 93-96°C) Yield 72%


(reaction completion time 7 h at 80 °C): IR (KBr, cm−1

) 3472, 3028, 2934,

2872, 2493, 1894, 1724, 1659, 1596, 1563, 1505. 1H NMR (400 MHz,

CDCl3) δ 7.91 (d, J = 8.4 Hz, 2H), 7.43 – 7.34 (m, 5H), 7.04 (d, J = 8.8 Hz,

2H), 5.13 (s, 2H), 5.09 (q, J = 7.2 Hz, 1H), 3.90 (s, 1H), 1.43 (d, J = 6.8 Hz,

3H); 13

C NMR (100 MHz, CDCl3) δ 200.61, 163.25, 135.87, 130.99, 128.69,

128.30, 127.43, 126.18, 114.86, 70.19, 68.84, 22.58; HRESI-MS (m/z) Calculated for C16H16O3 (M+

+ Na) 279.0997, found (M+ + Na) 279.0995.

4'-((4-(2-hydroxypropanoyl)phenoxy)methyl)-[1,1'-biphenyl]-2-carbonitrile (6g): Yellow solid;

(mp. 130-132°C) Yield 74% (199 mg); Rf (30% EtOAc/hexane) 0.2.

Prepared as shown in the general experimental procedure (reaction

completion time 8 h at 80 °C): IR (KBr, cm−1

) 3470, 3060, 2977, 2923,

2503, 2363, 2218, 2084, 1837, 1658, 1598, 1568, 1512; 1H NMR (400

MHz, CDCl3) δ 7.94 (d, J = 8.4 Hz, 2H), 7.77 (d, J = 7.2 Hz, 1H), 7.67 –

7.50 (m, 6H), 7.46 (t, J = 7.6 Hz, 1H), 7.07 (d, J = 8.4 Hz, 2H), 5.20 (s, 2H),


27

5.11 (q, J = 6.8 Hz, 1H), 1.45 (d, J = 6.8 Hz, 3H); 13

C NMR (100 MHz, CDCl3) δ 200.56, 163.05,

144.72, 138.02, 136.43, 133.69, 132.84, 131.00, 129.92, 129.04, 127.68, 127.65, 126.25, 118.57,

114.81, 111.07, 69.65, 68.80, 22.52; HRESI-MS (m/z) Calculated for C23H19NO3 (M+ + Na)

380.1263, found (M+ + Na) 380.1263.

2-hydroxy-1-(4-((4-nitrobenzyl)oxy)phenyl)propan-1-one (6h): Yellow solid; (mp. 110-113°C)

Yield 64% (144 mg); Rf (30% EtOAc/hexane) 0.3. Prepared as shown in the general experimental

procedure (reaction completion time 6 h at 80 °C): IR (KBr, cm−1

) 3709,

3417, 3077, 2973, 2929, 2362, 1976, 1671, 1598, 1568, 1511, 1341; 1H

NMR (400 MHz, CDCl3) δ 8.27 (d, J = 8.8 Hz, 2H), 7.94 (d, J = 8.8 Hz,

2H), 7.62 (d, J = 8.4 Hz, 2H), 7.05 (d, J = 8.8 Hz, 2H), 5.26 (s, 2H), 5.11 (q,

J = 6.8 Hz, 1H), 3.86 (s, 1H), 1.45 (d, J = 7.2 Hz, 3H); 13

C NMR (100 MHz,

CDCl3) δ 200.55, 162.42, 147.62, 143.26, 131.04, 127.59, 126.69, 123.84,

114.76, 68.85, 68.68, 22.44; HRESI-MS (m/z) Calculated for C16H15NO5 (M+ + Na) 324.0848, found

(M+ + Na) 324.0846.

4-(2-hydroxypropanoyl)phenyl benzoate (6i): White solid; (mp. 80-83°C) Yield 74% (150 mg); Rf


completion time 8 h at 80 °C): IR (KBr, cm−1

) 3387, 3065, 2978, 2926,

2856, 2668, 1921, 1730, 1677, 1593, 1503; 1H NMR (400 MHz, CDCl3) δ

8.20 (d, J = 7.2 Hz, 2H), 8.02 (d, J = 8.8 Hz, 2H), 7.66 (t, J = 7.2 Hz, 1H),

7.53 (t, J = 7.6 Hz, 2H), 7.38 (d, J = 8.8 Hz, 2H), 5.17 (q, J = 6.8 Hz, 1H),

3.85 (d, J = 6.0 Hz, 1H), 1.47 (d, J = 7.2 Hz, 3H); 13

C NMR (100 MHz,

CDCl3) δ 201.09, 164.46, 155.25, 134.01, 130.81, 130.34, 130.23, 128.81,

128.68, 122.27, 69.26, 22.27; HRESI-MS (m/z) Calculated for C16H14O4 (M+ + Na) 293.0790, found

(M+ + Na) 293.0792.

4-(2-hydroxypropanoyl)phenyl 2-fluorobenzoate (6j): Pale yellow solid; (mp. 88-91°C) Yield 71%



28


) 3743, 3466, 3075,

2980, 2925, 2851, 2186, 2075, 1980, 1744, 1680, 1598; 1H NMR (400

MHz, CDCl3) δ 8.11 (dt, J = 7.2, 1.2 Hz, 1H), 8.03 (d, J = 8.8 Hz, 2H), 7.67

– 7.61 (m, 1H), 7.40 (d, J = 8.8 Hz, 2H), 7.31 (t, J = 7.6 Hz, 1H), 7.26 –

7.21 (m, 1H), 5.17 (q, J = 6.8 Hz, 1H), 3.74 (s, 1H), 1.48 (d, J = 6.8 Hz,

3H); 13

C NMR (100 MHz, CDCl3) δ 201.10, 162.01 (d, J = 260 Hz), 162.01

(d, J = 4 Hz), 154.85, 135.75, 132.54, 130.96, 130.35, 124.26 (d, J = 4 Hz), 122.25, 117.42, 117.38 (d,

J = 9 Hz), 69.28, 22.26; HRESI-MS (m/z) Calculated for C16H13FO4 (M+ + Na) 311.0696, found (M

+

+ Na) 311.0701.

2-hydroxy-1-(4-phenoxyphenyl)pentan-1-one (6k): Pale yellow oily liquid; Yield 64% (130 mg); Rf



) 3474, 3062, 2959, 2931,

2871, 2366, 2043, 1674, 1584; 1H NMR (400 MHz, CDCl3) δ 7.90 (d, J =

8.8 Hz, 2H), 7.42 (t, J = 8.0 Hz, 2H), 7.23 (t, J = 7.2 Hz, 1H), 7.10 (d, J =

8.0 Hz, 2H), 7.02 (d, J = 8.8 Hz, 2H), 5.03 (dd, J = 8.0, 3.2 Hz, 1H), 3.71

(s, 1H), 1.85 – 1.80 (m, 1H), 1.56 – 1.51 (m, 2H), 1.49 – 1.40 (m, 1H),

0.93 (t, J = 7.2 Hz, 3H); 13

C NMR (100 MHz, CDCl3) δ 200.51, 162.76, 155.01, 130.85, 130.12,


C17H18O3 (M+ + Na) 293.1154, found (M

+ + Na) 293.1159.

2-hydroxy-1-(4-(phenylthio)phenyl)butan-1-one (6l): Pale yellow oily liquid; Yield 64% (131 mg);



) 3469, 3059, 2967, 2930,

2874, 2123, 1911, 1672, 1585; 1H NMR (400 MHz, CDCl3) δ 7.76 (d, J =

8.4 Hz, 2H), 7.54 – 7.52 (m, 2H), 7.43 – 7.26 (m, 3H), 7.19 (d, J = 8.4 Hz,

2H), 4.97 (dd, J = 6.4, 3.6 Hz, 1H), 3.71 (s, 1H), 1.95 – 1.87 (m, 1H), 1.64

– 1.53 (m, 1H), 0.92 (t, J = 7.6 Hz, 3H); 13



29

200.85, 146.66, 134.38, 131.09, 130.51, 129.76, 129.15, 128.96, 126.89, 73.70, 28.91, 8.82; HRESI-

MS (m/z) Calculated for C16H16O2S (M+ + Na) 295.0769, found (M

+ + Na) 295.0770.

2-hydroxy-1-(thiophen-2-yl)butan-1-one (8a): Yellow oily liquid; Yield 56% (71 mg); Rf (10%



) 3449, 3091, 2967, 2932, 2876, 2014, 1735,

1652, 1513; 1H NMR (400 MHz, CDCl3) δ 7.77 (dd, J = 3.6, 0.8 Hz, 1H), 7.74

(dd, J = 4.0, 0.8 Hz, 1H), 7.20 – 7.17 (m, 1H), 4.87 (dd, J = 6.8, 4.0 Hz, 1H),

3.55 (s, 1H), 2.07 – 1.97 (m, 1H), 1.79 – 1.68 (m, 1H), 0.99 (t, J = 7.2 Hz, 3H);

13C NMR (100 MHz, CDCl3) δ 194.48, 139.86, 134.65, 132.86, 128.31, 74.81, 29.80, 8.90; HRESI-

MS (m/z) Calculated for C8H10O2S (M+ + Na) 193.0299, found (M

+ + Na) 193.0297.

2-hydroxy-1-(5-methylthiophen-2-yl)butan-1-one (8b): Yellow oily liquid; Yield 65% (90 mg); Rf



) 3788, 3700, 3660, 3468, 2967,


6.85 (d, J = 4.0 Hz, 1H), 4.81 (dd, J = 6.8, 3.6 Hz, 1H), 2.56 (s, 3H), 2.04 –

1.94 (m, 1H), 1.77 – 1.68 (m, 1H), 0.98 (t, J = 7.2 Hz, 3H); 13

C NMR (100

MHz, CDCl3) δ 193.90, 150.96, 137.58, 133.52, 127.02, 74.42, 29.97, 15.98, 8.90; HRESI-MS (m/z)

Calculated for C9H12O2S (M+ + Na) 207.0456, found (M

+ + Na) 207.0455.

1-(5-bromothiophen-2-yl)-2-hydroxybutan-1-one (8c): Yellow oily liquid; Yield 60% (111 mg); Rf



) 3439, 3095, 2966, 2926,

2852, 2552, 2182, 2163, 1737, 1656, 1597; 1H NMR (400 MHz, CDCl3) δ

7.51 (d, J = 4.0 Hz, 1H), 7.15 (d, J = 4.0 Hz, 1H), 4.78 (dd, J = 7.2, 4.0 Hz,

1H), 3.44 (s, 1H), 2.03 – 1.93 (m, 1H), 1.77 – 1.66 (m, 1H), 0.98 (t, J = 7.2

Hz, 3H); 13

C NMR (100 MHz, CDCl3) δ 193.42, 141.31, 133.11, 131.39, 123.94, 74.67, 29.70, 8.91;

HRESI-MS (m/z) Calculated for C8H9BrO2S (M+ + Na) 270.9404, found (M

+ + Na) 270.9404.


30

2-hydroxy-1-(5-methylfuran-2-yl)butan-1-one (8d): Colourless oily

liquid; Yield 45% (51 mg); Rf (10% EtOAc/hexane) 0.1. Prepared as

shown in the general experimental procedure (reaction completion time 8 h

at 90 °C): IR (Neat, cm−1

) 3673, 3451, 3121, 2967, 2929, 2877, 2358,

1993, 1661, 1513; 1H NMR (400 MHz, CDCl3) δ 7.23 (d, J = 3.6 Hz, 1H), 6.22 (d, J = 3.6 Hz, 1H),

4.75 (dd, J = 6.8, 4.0 Hz, 1H), 3.54 (s, 1H), 2.42 (s, 3H), 2.02 – 1.92 (m, 1H), 1.76 – 1.65 (m, 1H),

0.98 (t, J = 7.6 Hz, 3H); 13

C NMR (100 MHz, CDCl3) δ 189.55, 158.67, 148.92, 120.86, 109.29,


+

+ Na) 191.0684.

2-hydroxy-1-(1-methyl-1H-indol-3-yl)butan-1-one (8e): Brown solid; (mp. 81-84°C) Yield 46%



) 3462, 2924, 2868,

2360, 1632, 1528, 1462, 1354; 1H NMR (400 MHz, CDCl3) δ 8.32 – 8.30

(m, 1H), 7.73 (s, 1H), 7.35 – 7.32 (m, 3H), 4.78 (dd, J = 6.8, 3.6 Hz, 1H),

3.85 (s, 3H), 3.26 (s, 1H), 2.04 – 1.94 (m, 1H), 1.76 – 1.66 (m, 1H), 0.99 (t, J

= 7.6 Hz, 3H); 13

C NMR (100 MHz, CDCl3) δ 195.90, 137.26, 135.58,

126.30, 123.65, 122.93, 122.30, 112.39, 109.84, 74.36, 33.65, 30.33, 9.03; HRESI-MS (m/z)

Calculated for C13H15NO2 (M+ + Na) 240.1000, found (M

+ + Na) 240.1001.

1-(1-benzoyl-1H-indol-3-yl)-2-hydroxybutan-1-one (8f): Brown oily liquid; Yield 52% (120 mg);



) 3373, 2930, 2846, 2159,

1920, 1697, 1659, 1541; 1H NMR (400 MHz, CDCl3) δ 8.34 – 8.31 (m,

1H), 8.25 – 8.21 (m, 1H), 8.00 (s, 1H), 7.77 (d, J = 7.2 Hz, 2H), 7.71 (t, J =

7.2 Hz, 1H), 7.60 (t, J = 7.6 Hz, 2H), 7.47 – 7.42 (m, 2H), 4.74 – 4.72 (m,

1H), 3.70 (d, J = 5.6 Hz, 1H), 1.98 – 1.91 (m, 1H), 1.74 – 1.65 (m, 1H),

0.95 (t, J = 7.2 Hz, 3H); 13

C NMR (100 MHz, CDCl3) δ 197.53, 168.41,

136.28, 133.39, 133.17, 132.98, 129.53, 129.02, 127.36, 126.23, 125.52, 122.32, 117.23, 115.86,


31

74.93, 29.76, 8.83; HRESI-MS (m/z) Calculated for C19H17NO3 (M+ + Na) 330.1106, found (M

+ +

Na) 330.1105.

1-(1-benzoyl-5-methoxy-1H-indol-3-yl)-2-hydroxybutan-1-one (8g): Brown oily liquid; Yield 64%



) 3470, 2966,

2935, 2836, 2076, 1697, 1658, 1537, 1475, 1451; 1H NMR (400 MHz,

CDCl3) δ 8.13 (d, J = 9.2 Hz, 1H), 7.95 (s, 1H), 7.82 (d, J = 2.4 Hz, 1H),

7.76 (d, J = 7.2 Hz, 2H), 7.70 (t, J = 7.2 Hz, 1H), 7.59 (t, J = 7.6 Hz,

2H), 7.04 (dd, J = 9.2, 2.8 Hz, 1H), 4.70 (dd, J = 6.4, 4.0 Hz, 1H), 3.92

(s, 3H), 3.69 (s, 1H), 1.99 – 1.89 (m, 1H), 1.73 – 1.63 (m, 1H), 0.95 (t, J

= 7.2 Hz, 3H); 13

C NMR (100 MHz, CDCl3) δ 197.60, 168.19, 157.87, 133.69, 133.05, 132.95,

130.74, 129.46, 128.97, 128.52, 116.92, 116.69, 115.52, 104.12, 74.81, 55.67, 29.89, , 8.85; HRESI-

MS (m/z) Calculated for C20H19NO4 (M+ + Na) 360.1212, found (M

+ + Na) 360.1212.


32

References

1. W.-B. Sheng, Q. Jiang, W.-P. Luo and C.-C. Guo, J. Org. Chem., 2013, 78, 5691-5693.

2. E. Rothstein and W. G. Schofield, J. Chem. Soc., 1965, 4566-4576.

3. R. Lin, F. Chen and N. Jiao, Org. Lett., 2012, 14, 4158-4161.

4. R. Takagi, N. Igata, K. Yamamoto and S. Kojima, J. Mol. Catal. A: Chem., 2010, 321, 71-76.

5. F. Wu, W. Lu, Q. Qian, Q. Ren and H. Gong, Org. Lett., 2012, 14, 3044-3047.

6. M. Nakamura, M. Miki and T. Majima, J. Chem. Soc. Perkin Trans., 1 2000, 415–420.

7. R. Lerebours, A. Camacho-Soto and C. Wolf, J. Org. Chem., 2005, 70, 8601-8604.

8. S. Scholz, H. Marschall-Weyerstahl and P. Weyerstahl, Liebigs Ann. Chem., 1985, 1935-1950.

9. Ž. Hodnik, L. Peterlin Mašič, T. Tomašić, D. Smodiš, C. D’Amore, S. Fiorucci and D. Kikelj, J.

Med. Chem., 2014, 57, 4819-4833.

10. M. Uchiyama, S. Furumoto, M. Saito, Y. Kondo and T. Sakamoto, J. Am. Chem. Soc., 1997,

119, 11425-11433.

11. A. S. Patil, D.-L. Mo, H.-Y. Wang, D. S. Mueller and L. L. Anderson, . Angew. Chem., Int. Ed.,

2012, 51, 7799-7803.

12. M. Koprowski, J. Łuczak and E. Krawczyk, Tetrahedron, 2006, 62, 12363-12374.

13. C. K. Jang, S. H. Kim and J.-Y. Jaung, Porphyrins Phthalocyanines, 2010, 14, 531-539.

14. A. Clerici and O. Porta, J. Org. Chem., 1993, 58, 2889-2893.

15. T. J. Houghton, K. S. E. Tanaka, T. Kang, E. Dietrich, Y. Lafontaine, D. Delorme, S. S. Ferreira,

F. Viens, F. F. Arhin, I. Sarmiento, D. Lehoux, I. Fadhil, K. Laquerre, J. Liu, V. Ostiguy, H.

Poirier, G. Moeck, T. R. Parr and A. R. Far, J. Med. Chem., 2008, 51, 6955-6969.

16. A. S. Demir, Ö. Şeşenoglu, E. Eren, B. Hosrik, M. Pohl, E. Janzen, D. Kolter, R. Feldmann, P.

Dünkelmann and M. Müller, Adv. Synth. Catal., 2002, 344, 96-103.

17. M. Y. Jin, S. M. Kim, H. Han, D. H. Ryu and J. W. Yang, Org. Lett., 2011, 13, 880-883.

18. G. W. Amarante, M. Cavallaro and F. Coelho, J. Braz. Chem. Soc., 2011, 22, 1568-1584.


33

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

-0.0

00

0.9

82

1.0

00

1.0

19

1.2

38

1.2

57

1.2

76

1.7

19

1.7

38

1.7

56

1.7

74

1.7

93

1.8

11

2.6

74

2.6

93

2.7

12

2.7

31

2.9

06

2.9

24

2.9

42

7.2

67

7.2

87

7.8

81

7.9

01

3.1

80

3.1

42

2.1

09

2.1

49

2.1

02

2.0

99

2.0

00


34

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

13.8

92

15.1

95

17.8

54

28.8

86

40.4

06

76.6

83

77.0

01

77.3

19

128.0

00

128.2

42

134.8

10

149.7

38

200.1

31


35

9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

0.8

60

0.8

77

0.8

94

0.9

81

1.0

00

1.0

18

1.2

56

1.3

01

1.3

12

1.5

85

1.6

03

1.6

21

1.6

39

1.6

57

1.7

18

1.7

37

1.7

55

1.7

74

1.7

92

1.8

10

2.6

29

2.6

49

2.6

68

2.9

03

2.9

21

2.9

39

7.2

42

7.2

61

7.8

68

7.8

89

3.1

23

3.1

39

14.7

67

2.2

58

2.0

82

2.0

58

2.0

53

2.1

20

2.0

00


36

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

13.9

00

14.0

87

17.8

55

22.6

57

29.2

42

29.2

96

29.4

33

29.5

35

29.5

72

31.1

14

31.8

71

35.9

53

40.3

99

76.6

83

77.0

01

77.3

18

128.1

57

128.5

42

134.8

01

148.5

29

200.1

09


37

10 9 8 7 6 5 4 3 2 1 0 ppm

0.9

19

0.9

37

0.9

55

1.3

44

1.3

62

1.3

80

1.3

99

1.4

18

1.4

35

1.6

61

1.6

80

1.6

98

1.7

18

1.7

36

2.8

97

2.9

15

2.9

34

4.0

11

7.1

57

7.1

76

7.2

05

7.2

23

7.2

48

7.2

68

7.2

85

7.3

04

7.8

67

7.8

87

3.2

44

2.1

87

2.2

74

2.0

75

2.0

00

2.3

61

5.1

85

2.0

13


38

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

13.9

01

22.4

40

26.4

87

38.1

99

41.8

19

76.6

83

77.0

00

77.3

18

126.3

27

128.3

26

128.3

83

128.5

57

128.8

78

129.0

17

135.1

00

140.0

32

146.4

53

200.1

37


39

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

0.9

27

0.9

45

0.9

64

1.3

53

1.3

71

1.3

89

1.4

08

1.4

26

1.4

45

1.6

65

1.6

84

1.7

03

1.7

21

1.7

40

1.8

06

2.7

96

2.8

06

2.8

98

2.9

16

2.9

35

7.1

08

7.1

29

7.2

52

7.6

56

7.6

65

3.1

42

2.2

02

2.2

94

4.0

79

4.0

73

2.0

42

1.0

00

1.8

92


40

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

13.8

99

22.4

59

22.7

92

22.9

27

26.6

23

29.3

35

29.5

40

38.1

56

76.6

83

77.0

01

77.3

19

125.1

10

128.8

86

129.2

02

134.5

55

137.2

98

142.8

02

200.5

22


41

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

1.0

11

1.0

30

1.0

48

1.6

73

1.7

57

1.7

75

1.7

94

1.8

12

1.8

30

1.8

49

2.9

71

2.9

89

3.0

08

3.9

31

7.2

50

7.3

43

7.3

61

7.3

82

7.4

04

7.4

22

7.5

61

7.5

79

7.8

00

7.8

19

7.8

36

7.9

86

8.0

05

8.1

32

3.0

98

2.0

64

2.0

51

2.0

68

2.0

38

1.0

26

2.0

34

1.0

35

1.0

00

7.47.67.88.08.2 ppm

7.250

7.343

7.361

7.382

7.404

7.422

7.561

7.579

7.800

7.819

7.836

7.986

8.005

8.132

2.038

1.026

2.034

1.035

1.000


42

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

13.9

27

17.9

53

36.8

59

40.6

31

76.6

82

77.0

00

77.3

18

119.5

97

120.7

87

124.6

69

125.2

00

126.9

94

127.3

66

127.8

94

135.5

17

140.5

01

143.2

44

144.4

33

146.1

50

200.2

76

125130135140145 ppm

119.597

120.787

124.669

125.200

126.994

127.366

127.894

135.517

140.501

143.244

144.433

146.150


43

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

1.0

09

1.0

28

1.0

46

1.7

56

1.7

75

1.7

93

1.8

11

1.8

30

1.8

48

2.9

58

2.9

76

2.9

94

7.2

22

7.3

71

7.3

90

7.4

08

7.4

57

7.4

76

7.4

95

7.6

72

7.6

91

7.7

52

7.7

72

7.7

85

7.8

13

8.0

47

8.0

67

3.0

77

2.0

58

2.0

23

2.0

77

4.0

62

4.0

62

5.0

62

2.0

00

7.47.67.88.0 ppm

7.222

7.371

7.390

7.408

7.457

7.476

7.495

7.672

7.691

7.752

7.772

7.785

7.813

8.047

8.067

2.077

4.062

4.062

5.062

2.000


44

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

13.8

97

17.7

98

40.5

52

76.6

83

77.0

00

77.3

18

125.1

24

125.9

74

127.2

98

127.3

71

127.6

73

128.6

65

128.8

70

135.9

74

140.7

98

142.5

28

145.3

71

199.9

51


45

10 9 8 7 6 5 4 3 2 1 0 ppm

0.9

58

0.9

76

0.9

95

1.6

98

1.7

17

1.7

36

1.7

54

1.7

72

1.7

91

2.8

71

2.8

89

2.9

08

5.5

77

7.0

81

7.0

99

7.1

89

7.2

08

7.2

23

7.2

54

7.2

73

7.2

91

7.8

62

7.8

82

3.0

48

2.1

42

2.0

00

1.0

31

4.1

02

4.0

10

4.1

84

1.9

71


46

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

13.8

32

17.6

95

40.3

59

56.6

73

76.6

81

76.9

99

77.3

17

126.5

20

128.0

80

128.3

81

129.2

86

129.5

42

135.2

19

142.9

39

149.1

32

199.8

89


47

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

1.0

14

1.0

33

1.0

51

1.7

60

1.7

79

1.7

97

1.8

16

1.8

34

1.8

52

2.9

67

2.9

86

3.0

04

7.2

46

7.3

90

7.4

07

7.4

26

7.4

71

7.4

90

7.5

08

7.6

72

7.6

90

7.7

53

7.7

73

7.8

00

7.8

26

8.0

58

8.0

78

6.0

66

4.1

09

4.0

01

1.0

74

2.1

62

2.0

53

7.0

31

4.0

00


48

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

13.8

68

17.7

64

40.5

42

76.6

83

77.0

00

77.3

18

125.0

95

125.9

38

127.2

67

127.3

60

127.8

24

128.6

87

128.9

16

136.0

88

140.4

95

141.2

36

142.7

43

145.0

38

199.8

75


49

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

01

0.9

60

0.9

68

0.9

87

1.0

05

1.7

08

1.7

27

1.7

46

1.7

64

1.7

82

2.8

94

2.9

12

2.9

30

5.6

35

7.0

79

7.0

97

7.1

90

7.2

10

7.2

42

7.2

58

7.2

85

7.3

03

7.3

21

7.8

88

7.9

08

6.3

20

4.2

21

4.2

07

1.0

42

2.1

11

7.1

82

4.0

00


50

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

13.7

98

17.6

56

40.3

64

56.5

75

76.6

82

77.0

00

77.3

18

126.8

17

128.1

96

128.5

40

129.2

05

129.4

76

135.4

55

142.1

18

148.1

77

199.8

04


51

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

1.0

20

1.0

39

1.0

57

1.7

68

1.7

86

1.8

04

1.8

22

1.8

41

1.8

59

2.9

82

3.0

01

3.0

19

7.2

66

7.7

69

7.7

89

7.8

58

8.0

76

8.0

97

9.2

32

6.3

86

6.2

54

6.0

00

3.0

61

6.0

51


52

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

13.8

62

17.7

57

40.5

62

76.6

83

77.0

00

77.3

18

125.9

50

127.3

88

128.7

34

136.2

26

141.5

00

144.7

55

199.8

51


53

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

1.1

97

1.2

15

1.2

33

2.9

31

2.9

49

2.9

67

2.9

86

5.1

89

7.0

22

7.0

43

7.2

60

7.4

36

7.4

54

7.4

73

7.5

06

7.5

26

7.5

46

7.5

66

7.5

88

7.6

08

7.6

34

7.6

53

7.6

72

7.7

61

7.7

80

7.9

58

7.9

80

3.0

65

2.0

39

2.0

35

2.0

00

1.0

34

5.1

26

1.0

39

1.0

28

2.0

21

7.57.67.77.87.98.0 ppm

7.436

7.454

7.473

7.506

7.526

7.546

7.566

7.588

7.608

7.634

7.653

7.672

7.761

7.780

7.958

7.980

1.034

5.126

1.039

1.028

2.021


54

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

8.3

71

31.3

84

69.5

74

76.6

83

77.0

00

77.3

18

111.1

66

114.4

58

118.6

14

127.6

89

129.0

42

129.9

82

130.2

23

130.2

80

132.8

54

133.7

34

136.7

90

137.9

64

144.8

52

162.2

44

199.4

13

128130132134136138140142144 ppm

127.689

129.042

129.982

130.223

130.280

132.854

133.734

136.790

137.964

144.852


55

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

1.1

97

1.2

15

1.2

33

2.9

33

2.9

51

2.9

70

2.9

88

5.2

44

6.9

95

7.0

16

7.2

68

7.6

08

7.6

29

7.9

57

7.9

79

8.2

51

8.2

72

3.1

05

2.0

39

2.0

37

2.0

08

2.0

00

2.0

10

2.0

01


56

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

8.3

32

31.4

46

68.6

45

76.6

83

77.0

00

77.3

18

114.4

29

123.8

86

127.6

01

130.2

96

130.7

24

143.6

03

147.6

79

161.6

18

199.3

45


57

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

1.2

27

1.2

45

1.2

63

2.9

94

3.0

12

3.0

30

3.0

48

7.2

61

7.3

16

7.3

38

7.5

10

7.5

29

7.5

48

7.6

43

7.6

61

7.6

80

8.0

51

8.0

72

8.1

99

8.2

18

3.0

42

2.0

23

2.0

13

2.0

67

1.0

16

2.0

48

2.0

00


58

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

8.2

04

31.7

81

76.6

82

77.0

00

77.3

18

121.8

76

128.6

49

129.0

38

129.6

32

130.2

21

133.8

82

134.5

45

154.4

68

164.6

41

199.5

63


59

10 9 8 7 6 5 4 3 2 1 0 ppm

-0.0

00

1.2

27

1.2

45

1.2

63

2.9

97

3.0

15

3.0

33

3.0

51

7.1

52

7.1

76

7.2

04

7.2

27

7.2

52

7.2

65

7.2

76

7.2

95

7.3

14

7.3

33

7.3

54

7.5

77

7.6

06

7.6

21

7.6

36

7.6

53

8.0

20

8.0

51

8.0

72

8.0

90

8.1

09

8.1

28

2.8

84

1.9

02

4.1

46

1.0

54

3.0

00


60

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

8.1

72

31.7

73

76.6

83

77.0

00

77.3

18

117.1

47

117.3

68

117.5

03

117.5

94

121.8

23

124.1

83

124.2

22

129.6

21

132.5

12

132.6

96

134.6

23

135.4

99

135.5

92

154.0

65

161.0

18

162.1

45

162.1

85

163.6

21

199.6

26


61

10 9 8 7 6 5 4 3 2 1 0 ppm

-0.0

00

0.9

32

0.9

51

0.9

69

1.3

60

1.3

78

1.3

97

1.4

16

1.4

34

1.4

53

1.6

77

1.6

96

1.7

14

1.7

33

1.7

52

2.9

03

2.9

21

2.9

40

6.9

85

7.0

06

7.0

57

7.0

77

7.1

75

7.1

93

7.2

11

7.2

58

7.3

72

7.3

91

7.4

11

7.9

33

7.9

54

3.2

07

2.1

34

2.0

68

2.0

76

2.3

04

2.0

66

1.0

60

2.0

74

2.0

00


62

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

13.9

26

22.4

91

26.6

21

38.1

13

76.6

83

77.0

00

77.3

18

117.2

91

120.0

96

124.5

15

130.0

06

130.2

89

131.7

77

155.5

40

161.7

34

199.1

89


63

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

0.9

64

0.9

82

1.0

01

1.6

95

1.7

15

1.7

34

1.7

52

1.7

70

1.7

88

2.8

58

2.8

77

2.8

95

7.1

98

7.2

18

7.3

82

7.3

94

7.4

80

7.4

90

7.8

12

7.8

32

3.0

94

2.3

41

1.9

65

2.2

82

3.0

79

2.0

01

2.0

00


64

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

13.8

40

17.7

73

40.3

19

76.6

83

77.0

00

77.3

18

127.5

19

128.5

99

128.6

68

129.6

07

132.1

80

133.7

22

134.3

96

144.4

22

199.3

99


65

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

0.9

70

0.9

89

1.0

07

1.8

90

2.5

24

2.7

90

2.8

09

2.8

27

6.7

83

6.7

91

7.2

81

7.5

17

7.5

26

3.1

16

2.0

67

3.0

69

2.0

63

1.0

00

1.0

05


66

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

13.7

95

15.9

10

18.3

05

40.7

03

76.6

83

77.0

01

77.3

19

126.5

79

132.2

19

142.2

65

149.2

79

193.0

74


67

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

0.9

74

0.9

93

1.0

11

1.7

12

1.7

30

1.7

48

1.7

66

1.7

85

1.8

03

2.7

85

2.8

03

2.8

21

7.0

88

7.0

97

7.4

35

7.4

44

3.1

75

2.2

17

2.0

95

1.0

00

1.0

11


68

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

13.7

60

18.0

36

40.5

16

76.6

82

77.0

00

77.3

18

122.2

35

131.1

08

131.7

07

145.9

05

192.2

64


69

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

1.0

00

1.0

19

1.0

37

1.7

48

1.7

67

1.7

85

1.8

04

1.8

22

1.8

41

1.8

59

2.8

01

2.8

20

2.8

38

3.8

45

7.2

58

7.2

87

7.3

02

7.3

07

7.3

19

7.3

30

7.3

44

7.7

20

8.3

86

8.3

94

8.4

07

3.0

87

2.1

67

2.0

73

3.1

16

3.0

90

1.0

09

1.0

00

7.47.67.88.08.28.4 ppm

7.258

7.287

7.302

7.307

7.319

7.330

7.344

7.720

8.386

8.394

8.407

3.090

1.009

1.000


70

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

14.0

15

18.5

79

33.3

49

41.7

49

76.6

83

77.0

00

77.3

18

109.4

94

116.4

91

122.3

55

122.4

86

123.1

34

126.2

29

135.1

98

137.3

41

195.8

13


71

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

0.9

54

0.9

72

0.9

91

1.7

11

1.7

29

1.7

48

1.7

66

1.7

84

1.8

02

2.7

41

2.7

59

2.7

77

7.2

55

7.3

85

7.3

94

7.3

99

7.4

07

7.5

56

7.5

75

7.5

94

7.6

55

7.6

73

7.6

92

7.7

53

7.7

71

7.9

27

8.2

15

8.2

23

8.2

37

8.3

83

8.3

90

8.3

98

8.4

05

3.0

74

2.0

18

2.0

45

2.0

09

2.0

87

1.1

69

2.1

02

1.0

70

0.9

71

1.0

00


72

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

13.7

64

17.7

68

41.7

94

76.6

83

77.0

01

77.3

19

115.7

12

121.0

05

122.5

27

125.1

65

125.7

62

127.5

47

128.8

58

129.3

48

132.7

01

132.7

39

133.2

97

136.3

70

168.4

80

196.4

14


73

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

0.9

63

0.9

82

1.0

00

1.7

20

1.7

38

1.7

56

1.7

75

1.7

93

1.8

11

2.7

39

2.7

57

2.7

75

3.9

03

6.9

94

7.0

00

7.0

16

7.0

22

7.2

66

7.5

64

7.5

83

7.6

02

7.6

61

7.6

79

7.6

98

7.7

53

7.7

72

7.8

89

7.9

10

7.9

15

8.1

21

8.1

44

3.0

96

2.2

45

2.0

59

3.0

98

1.0

00

2.0

26

1.0

75

2.0

15

0.9

46

1.0

35

1.0

10

7.47.67.88.08.2 ppm

7.266

7.564

7.583

7.602

7.661

7.679

7.698

7.753

7.772

7.889

7.910

7.915

8.121

8.144

2.026

1.075

2.015

0.946

1.035

1.010


74

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

13.8

11

17.7

86

41.6

39

55.6

07

76.6

82

77.0

00

77.3

19

104.2

68

115.2

34

116.5

98

120.8

13

128.7

01

128.8

72

129.3

36

130.9

14

132.6

75

133.0

65

133.3

39

157.6

79

168.3

03

196.6

66


75

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

1.4

49

1.4

66

3.8

10

3.8

26

5.1

38

5.1

55

5.1

72

5.1

89

5.2

06

7.2

70

7.4

91

7.5

10

7.5

29

7.6

09

7.6

27

7.6

45

7.9

25

7.9

44

3.0

45

0.9

45

1.0

10

2.0

07

1.0

00

2.0

06


76

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

22.0

61

69.1

72

76.6

80

76.9

99

77.3

17

128.5

00

128.7

06

133.1

71

133.8

25

202.2

23


77

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

-0.0

00

0.9

25

0.9

44

0.9

62

1.5

65

1.5

83

1.6

01

1.6

19

1.6

37

1.6

54

1.6

73

1.9

10

1.9

19

1.9

29

1.9

38

1.9

47

1.9

56

1.9

64

1.9

74

1.9

82

1.9

92

2.0

01

2.0

11

5.0

55

5.0

64

5.0

72

5.0

81

7.2

68

7.4

86

7.5

05

7.5

24

7.6

05

7.6

23

7.6

42

7.9

09

7.9

27

3.1

16

1.0

66

1.0

76

1.0

00

2.0

69

1.0

25

2.0

45


78

220 200 180 160 140 120 100 80 60 40 20 0 ppm

8.8

2

28.8

1

73.9

3

76.6

8

77.0

0

77.3

2

128.4

7

128.8

4

133.7

2

133.9

0

202.1

0


79

9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

0.9

00

0.9

18

0.9

36

1.4

00

1.4

18

1.4

25

1.4

36

1.4

45

1.4

52

1.4

63

1.4

71

1.4

88

1.5

11

1.5

20

1.5

31

1.5

41

1.5

52

1.5

59

1.5

71

1.5

76

1.7

98

1.8

07

1.8

15

1.8

28

1.8

35

1.8

51

1.8

61

5.0

80

5.0

89

5.0

98

5.1

06

7.2

79

7.4

84

7.5

03

7.5

22

7.6

01

7.6

20

7.6

38

7.9

06

7.9

26

3.1

44

1.0

83

2.1

50

1.0

34

1.0

06

2.1

00

1.0

15

2.0

00


80

220 200 180 160 140 120 100 80 60 40 20 0 ppm

13.7

6

18.1

7

37.8

8

72.8

7

76.6

8

77.0

0

77.3

2

128.4

5

128.7

9

133.6

1

133.8

4

202.1

4


81

9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

0.8

26

0.8

37

0.8

42

0.8

54

1.1

12

1.1

19

1.1

28

1.1

36

1.1

43

1.1

51

1.1

68

1.1

77

1.1

81

1.1

88

1.1

93

1.2

06

1.3

71

1.3

80

1.3

85

1.3

96

1.4

11

1.4

22

1.4

68

1.4

84

1.5

00

1.5

07

1.5

17

1.5

26

1.5

35

1.5

45

1.8

10

1.8

18

1.8

31

1.8

37

1.8

44

1.8

57

1.8

65

3.7

08

3.7

24

5.0

60

5.0

77

5.0

85

5.1

01

7.2

68

7.4

87

7.5

06

7.5

25

7.6

03

7.6

22

7.6

40

7.9

05

7.9

24

6.0

64

2.1

69

1.2

36

3.0

99

1.0

57

0.9

67

1.0

24

2.0

48

1.0

08

2.0

00


82

220 200 180 160 140 120 100 80 60 40 20 0 ppm

22.3

7

22.5

9

22.7

6

27.8

3

36.1

1

38.5

6

73.1

3

76.6

8

77.0

0

77.3

2

128.4

8

128.8

3

133.6

8

133.8

7

202.1

8


83

-18 7 6 5 4 3 2 1 0 ppm

0.0

00

0.8

43

0.8

61

0.8

77

1.2

30

1.2

71

1.2

89

1.3

08

1.3

68

1.3

79

1.3

89

1.4

69

1.4

86

1.4

94

1.5

10

1.5

27

1.5

38

1.5

48

1.5

58

1.5

98

1.8

13

1.8

31

1.8

39

1.8

53

1.8

77

1.8

85

1.8

95

3.6

84

3.7

00

5.0

56

5.0

73

5.0

80

5.0

89

7.2

62

7.4

88

7.5

07

7.5

26

7.6

05

7.6

23

7.6

42

7.9

05

7.9

23

3.1

81

10.6

86

1.1

74

2.0

97

1.0

34

0.9

03

1.0

13

2.0

37

1.0

06

2.0

00


84

220 200 180 160 140 120 100 80 60 40 20 0 ppm

14.0

5

22.5

9

24.8

8

29.1

3

29.3

2

29.3

4

31.7

8

35.8

7

73.1

1

76.6

8

77.0

0

77.3

2

128.4

9

128.8

3

133.6

9

133.8

7

202.1

9


85

8 7 6 5 4 3 2 1 0 ppm

-0.0

00

0.9

21

0.9

39

0.9

58

1.2

52

1.2

71

1.2

90

1.5

63

1.5

81

1.5

99

1.6

16

1.6

34

1.6

52

1.6

70

1.9

06

1.9

16

1.9

25

1.9

34

1.9

43

1.9

53

1.9

60

1.9

70

1.9

79

1.9

88

1.9

98

2.0

07

2.6

96

2.7

15

2.7

34

2.7

53

3.7

66

5.0

29

5.0

39

5.0

46

5.0

56

7.2

72

7.3

10

7.3

30

7.8

37

7.8

57

3.1

96

3.3

35

1.1

62

1.0

88

2.1

81

0.7

74

1.0

00

2.0

24

2.0

00


86

220 200 180 160 140 120 100 80 60 40 20 0 ppm

8.8

1

15.0

3

28.9

4

28.9

7

73.7

6

76.6

8

77.0

0

77.3

2

128.3

0

128.6

9

131.2

8

151.0

4

201.5

8


87

9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

0.9

27

0.9

46

0.9

64

1.3

51

1.5

68

1.5

86

1.6

04

1.6

21

1.6

39

1.6

57

1.6

75

1.9

17

1.9

26

1.9

36

1.9

45

1.9

54

1.9

63

1.9

71

1.9

81

1.9

90

1.9

99

2.0

08

2.0

18

3.7

59

5.0

34

5.0

43

5.0

50

5.0

59

7.2

69

7.5

00

7.5

21

7.8

52

7.8

73

3.2

41

9.3

62

1.1

43

1.1

06

0.9

09

1.0

49

2.0

08

2.0

00


88

220 200 180 160 140 120 100 80 60 40 20 0 ppm

8.8

3

28.9

0

30.9

5

35.1

6

73.7

6

76.6

8

77.0

0

77.3

2

125.7

4

128.4

3

130.9

7

157.7

6

201.5

2


89

9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

0.9

12

0.9

29

0.9

47

1.3

55

1.4

31

1.4

47

1.4

55

1.4

72

1.4

85

1.5

09

1.5

17

1.5

40

1.5

57

1.5

79

1.8

17

1.8

45

1.8

91

5.0

53

5.0

60

5.0

70

5.0

78

7.2

64

7.5

03

7.5

24

7.8

50

7.8

71

3.2

43

9.7

14

1.2

61

2.3

16

1.0

26

1.0

15

2.0

59

2.0

00


90

220 200 180 160 140 120 100 80 60 40 20 0 ppm

13.8

1

18.2

7

31.0

0

35.2

2

38.1

2

72.7

7

76.6

8

77.0

0

77.3

2

125.7

9

128.4

9

130.9

2

157.8

0

201.6

7


91

-19 8 7 6 5 4 3 2 1 0 ppm

-0.0

00

0.8

60

0.8

77

0.8

93

0.9

23

0.9

42

0.9

60

1.2

58

1.3

11

1.5

79

1.5

97

1.6

15

1.6

32

1.6

50

1.6

68

1.9

07

1.9

17

1.9

26

1.9

35

1.9

44

1.9

54

1.9

62

1.9

71

1.9

80

1.9

89

1.9

98

2.0

08

2.6

50

2.6

70

2.6

89

5.0

24

5.0

34

5.0

41

5.0

51

7.2

68

7.2

86

7.3

06

7.8

26

7.8

46

3.1

43

3.0

96

14.8

44

3.0

55

1.0

14

2.0

58

1.0

00

1.9

54

1.9

70


92

220 200 180 160 140 120 100 80 60 40 20 0 ppm

8.8

5

14.0

8

22.6

4

28.9

7

29.2

4

29.2

8

29.4

1

29.5

1

29.5

6

31.0

1

31.8

5

36.0

6

73.7

6

76.6

8

77.0

0

77.3

2

128.6

2

128.8

4

131.2

4

149.8

8

201.5

7


93

10 9 8 7 6 5 4 3 2 1 0 ppm

0.9

12

0.9

30

1.2

69

1.3

91

1.4

10

1.4

27

1.4

35

1.4

52

1.4

64

1.4

89

1.4

98

1.5

10

1.5

20

1.5

37

1.5

56

1.5

75

1.7

90

1.8

18

1.8

43

3.6

93

4.0

49

5.0

30

5.0

37

5.0

46

5.0

53

7.1

83

7.2

01

7.2

37

7.2

58

7.3

03

7.3

17

7.3

23

7.8

28

7.8

48

3.1

21

1.1

87

2.1

63

1.0

38

0.8

07

2.1

09

1.0

30

2.1

32

1.3

14

4.1

68

2.0

00


94

220 200 180 160 140 120 100 80 60 40 20 0 ppm

13.8

0

18.2

4

38.0

7

41.9

5

72.8

1

76.6

8

77.0

0

77.3

2

126.5

2

128.6

7

128.8

3

128.9

7

129.3

2

131.6

1

139.6

6

147.8

2

201.6

7


95

9 8 7 6 5 4 3 2 1 0 ppm

0.8

98

0.9

16

0.9

33

1.3

79

1.3

98

1.4

04

1.4

17

1.4

23

1.4

42

1.4

78

1.5

03

1.5

11

1.5

30

1.5

40

1.5

49

1.5

74

1.7

98

1.8

28

1.8

44

2.8

27

2.8

43

3.7

30

5.0

35

5.0

43

5.0

51

5.0

59

7.1

60

7.1

80

7.2

65

7.5

94

7.6

15

7.6

29

3.1

76

1.1

72

2.0

44

5.4

07

4.4

47

0.7

55

1.0

36

1.0

64

1.0

00

1.0

01


96

220 200 180 160 140 120 100 80 60 40 20 0 ppm

13.8

2

18.1

4

22.6

6

22.7

9

29.3

1

29.6

7

38.1

4

72.6

9

76.6

8

77.0

0

77.3

2

125.5

0

129.3

5

129.5

0

131.0

2

137.8

3

144.2

4

201.9

5


97

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

0.9

53

0.9

71

0.9

90

1.6

11

1.6

28

1.6

46

1.6

64

1.6

82

1.6

99

1.7

17

1.9

51

1.9

69

1.9

78

1.9

87

1.9

96

2.0

03

2.0

14

2.0

22

2.0

32

2.0

50

3.8

25

3.9

37

5.0

99

5.1

08

5.1

13

5.1

23

7.2

53

7.3

67

7.3

84

7.4

00

7.4

15

7.4

33

7.5

70

7.5

87

7.8

23

7.8

42

7.9

25

7.9

45

8.0

85

3.0

48

1.0

56

1.0

68

0.7

01

2.0

72

1.0

00

2.0

34

1.0

19

2.0

27

1.0

05

0.9

79


98

220 200 180 160 140 120 100 80 60 40 20 0 ppm

8.8

6

29.0

4

36.8

1

73.8

6

76.6

8

77.0

0

77.3

2

119.8

3

120.9

4

125.0

7

125.2

3

127.0

9

127.8

1

128.3

0

131.8

4

140.1

3

143.4

4

144.4

4

147.2

7

201.6

9


99

9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

0.9

64

0.9

82

1.0

01

1.5

95

1.6

25

1.6

43

1.6

61

1.6

79

1.6

96

1.7

14

1.9

65

1.9

75

1.9

84

1.9

93

2.0

02

2.0

12

2.0

19

2.0

29

2.0

38

2.0

47

2.0

56

2.0

66

3.7

47

5.1

01

5.1

11

5.1

18

5.1

28

7.2

55

7.3

95

7.4

13

7.4

32

7.4

80

7.4

99

7.5

17

7.6

91

7.7

09

7.8

04

7.8

07

7.8

16

7.8

37

7.8

46

7.8

49

8.0

23

8.0

43

3.0

14

1.2

66

1.0

59

0.7

70

1.0

00

2.0

88

4.1

34

4.1

41

5.0

78

2.0

49


100

220 200 180 160 140 120 100 80 60 40 20 0 ppm

8.8

8

28.9

3

73.9

7

76.6

8

77.0

0

77.3

2

125.1

6

126.2

8

127.3

1

127.6

9

127.7

6

128.9

2

129.1

5

132.5

5

140.7

1

142.6

5

146.5

8

201.6

0


101

9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

0.9

19

0.9

38

0.9

56

1.5

45

1.5

63

1.5

81

1.5

98

1.6

16

1.6

34

1.6

52

1.8

97

1.9

06

1.9

15

1.9

24

1.9

34

1.9

43

1.9

50

1.9

60

1.9

69

1.9

78

1.9

88

3.6

80

4.9

96

5.0

05

5.0

13

5.0

22

5.5

98

7.0

92

7.1

11

7.2

18

7.2

39

7.2

55

7.2

60

7.2

83

7.3

02

7.3

20

7.8

27

7.8

47

3.0

38

1.0

70

1.0

42

0.8

13

1.0

16

1.0

18

4.1

34

8.2

60

2.0

00

7.07.27.47.67.8 ppm

7.092

7.111

7.218

7.239

7.255

7.260

7.283

7.302

7.320

7.827

7.847

4.134

8.260

2.000


102

200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

8.9

08

28.8

91

56.8

15

73.8

64

76.6

83

77.0

01

77.3

19

126.6

99

128.5

01

128.5

95

129.3

26

129.8

74

131.7

65

142.6

96

150.5

03

201.5

45


103

9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

2.8

67

2.8

84

2.9

02

2.9

20

3.1

67

3.1

78

3.2

03

3.2

13

3.7

20

5.3

18

5.3

29

5.3

43

7.1

10

7.1

26

7.2

04

7.2

17

7.2

21

7.2

29

7.2

47

7.2

64

7.4

87

7.5

06

7.5

25

7.6

08

7.6

27

7.6

45

7.9

11

7.9

29

1.0

43

1.0

47

0.8

81

1.0

40

2.0

00

3.0

73

2.0

93

1.0

15

2.0

39


104

220 200 180 160 140 120 100 80 60 40 20 0 ppm

41.8

7

73.6

9

76.6

8

77.0

0

77.3

2

126.7

6

128.2

7

128.5

6

128.9

0

129.3

9

133.8

0

133.9

6

136.4

2

200.9

7


105

10 9 8 7 6 5 4 3 2 1 0 ppm

-0.0

00

1.4

65

1.4

82

3.6

99

5.1

64

5.1

81

5.1

99

5.2

16

7.2

73

7.6

53

7.6

73

7.6

92

7.8

78

7.8

97

8.1

02

8.1

21

8.2

00

3.2

29

0.9

35

1.0

53

1.0

53

1.0

36

1.0

25

1.0

00


106

200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

21.9

10

69.5

23

76.6

82

77.0

01

77.3

18

119

.383

122

.095

124

.804

125

.378

125

.419

125

.456

125

.494

127

.511

129

.545

130

.221

130

.257

130

.293

130

.329

131

.127

131

.442

131

.689

131

.700

131

.780

132

.098

134

.028

201

.171

122124126128130132134 ppm

119.383

122.095

124.804

125.378

125.419

125.456

125.494

127.511

129.545

130.221

130.257

130.293

130.329

131.127

131.442

131.689

131.700

131.780

132.098

134.028


107

-160-140-120-100-80-60-40-200 ppm

-62.9

62


108

10 9 8 7 6 5 4 3 2 1 ppm

0.0

00

0.9

67

0.9

85

1.0

03

1.6

44

1.6

62

1.6

80

1.6

98

1.7

16

1.9

84

1.9

94

2.0

02

2.0

12

2.0

19

2.0

29

2.0

38

2.0

47

3.7

22

5.1

04

5.1

13

5.1

20

5.1

29

7.2

60

7.4

17

7.4

34

7.4

52

7.4

95

7.5

14

7.5

32

7.6

90

7.7

09

7.8

18

7.8

38

7.8

70

8.0

36

8.0

57

6.1

52

2.3

67

2.0

88

1.5

17

1.9

76

1.0

52

2.0

03

2.0

04

7.0

00

4.0

15

7.27.47.67.88.08.2 ppm7.260

7.417

7.434

7.452

7.495

7.514

7.532

7.690

7.709

7.818

7.838

7.870

8.036

8.057

1.052

2.003

2.004

7.000

4.015


109

200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

8.8

68

28.9

09

74.0

00

76.6

82

77.0

00

77.3

17

125.1

77

126.2

84

127.2

94

127.7

07

128.0

02

129.0

10

129.2

08

132.7

90

140.3

38

141.0

80

143.0

11

146.1

43

201.5

83


110

10 9 8 7 6 5 4 3 2 1 0 ppm

0.9

27

0.9

46

0.9

64

1.5

54

1.5

71

1.5

89

1.6

07

1.6

25

1.6

43

1.6

61

1.9

05

1.9

15

1.9

23

1.9

33

1.9

42

1.9

51

1.9

59

1.9

68

1.9

77

1.9

86

2.0

05

3.7

02

5.0

09

5.0

19

5.0

24

5.0

32

5.6

60

7.0

89

7.1

07

7.2

37

7.2

58

7.2

80

7.2

98

7.3

19

7.3

38

7.3

55

7.8

58

7.8

78

6.0

85

2.1

10

2.0

67

1.9

47

2.0

18

1.0

09

2.0

48

4.2

30

3.0

33

4.0

00

7.27.4 ppm

7.089

7.107

7.237

7.258

7.280

7.298

7.319

7.338

7.355

2.048

4.230

3.033


111

200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

8.9

09

28.8

58

56.7

89

73.9

16

76.6

82

77.0

00

77.3

17

127.1

56

128.7

67

128.7

84

129.2

59

129.8

23

132.1

66

141.6

06

149.1

95

201.4

84

128130132 ppm

127.156

128.767

128.784

129.259

129.823

132.166


112

9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

1.2

54

1.3

04

1.3

49

1.3

61

1.4

27

1.4

95

1.5

23

1.5

39

1.5

58

1.5

63

1.6

88

1.7

05

1.7

22

1.8

43

1.8

52

1.8

68

1.8

88

1.8

96

2.9

16

2.9

34

2.9

52

3.6

83

5.0

65

5.0

73

5.0

82

5.0

90

7.2

63

7.4

34

7.4

53

7.4

72

7.4

88

7.5

06

7.5

26

7.5

52

7.5

70

7.6

03

7.6

21

7.6

40

7.9

02

7.9

21

7.9

29

7.9

31

7.9

50

7.9

70

7.9

90

5.4

65

2.4

03

2.2

23

1.2

09

1.8

78

0.8

31

1.0

31

5.1

24

1.1

23

4.0

00


113

220 200 180 160 140 120 100 80 60 40 20 0 ppm

24.1

0

24.7

5

29.0

7

29.1

4

35.7

6

38.4

1

73.0

0

76.6

8

77.0

0

77.3

2

127.9

6

128.4

6

128.4

9

128.8

3

132.8

4

133.5

8

133.8

9

136.9

4

200.3

8

202.0

7


114

-18 7 6 5 4 3 2 1 0 ppm

-0.0

00

1.2

30

1.2

43

1.2

54

1.2

76

1.2

94

1.3

10

1.3

30

1.3

38

1.3

47

1.3

56

1.3

73

1.4

01

1.4

25

1.4

52

1.4

82

1.4

95

1.5

04

1.5

23

1.5

39

1.5

47

1.8

00

1.8

09

1.8

25

1.8

31

1.8

53

1.8

63

3.1

78

3.6

74

4.3

94

4.3

95

5.0

25

5.0

37

5.0

44

5.0

51

5.0

63

7.2

70

7.4

76

7.4

95

7.5

15

7.5

99

7.6

19

7.6

38

7.8

78

7.8

97

4.2

83

4.2

47

2.0

69

1.5

84

2.0

43

4.0

53

2.0

00

3.9

99


115

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

24.5

83

24.7

53

28.8

82

29.0

28

35.5

90

35.6

97

72.9

02

72.9

67

76.6

81

76.9

99

77.3

17

128.4

56

128.8

51

133.5

56

133.9

31

202.0

23


116

-0.58.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

-0.0

00

0.9

67

0.9

85

1.0

04

1.0

25

1.0

44

1.0

62

1.6

64

1.6

82

1.7

00

1.7

18

1.7

35

1.7

75

1.7

93

1.8

11

1.8

29

1.8

48

1.8

66

1.9

87

1.9

96

2.0

05

2.0

14

2.0

22

2.0

32

2.0

50

2.9

94

3.0

12

3.0

30

3.7

29

3.7

45

5.1

02

5.1

17

5.1

27

5.1

43

7.2

64

7.7

80

7.8

01

7.8

20

7.8

40

7.8

71

7.8

88

8.0

45

8.0

65

8.0

88

8.1

09

3.2

55

6.0

56

1.3

69

4.0

02

1.1

92

4.0

21

1.0

69

1.0

58

4.0

00

2.2

73

2.1

33

1.1

09

2.1

71

4.0

33

7.98.08.1 ppm

7.780

7.801

7.820

7.840

7.871

7.888

8.045

8.065

8.088

8.109

4.000

2.273

2.133

1.109

2.171

4.033


117

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

8.8

72

13.8

99

17.8

06

28.9

15

40.6

29

74.0

22

76.6

81

76.9

99

77.3

17

126.0

26

126.3

00

127.4

48

127.7

48

128.8

10

129.2

41

132.8

91

136.3

54

141.2

61

141.6

90

144.7

21

145.9

87

199.9

39

201.5

85


118

10 9 8 7 6 5 4 3 2 1 0 ppm

-0.0

00

1.4

34

1.4

52

3.7

25

5.0

90

5.1

07

5.1

25

5.1

42

7.2

77

7.6

44

7.6

65

7.7

88

7.8

09

3.1

92

0.8

54

1.0

34

2.0

00

2.0

25


119

220 200 180 160 140 120 100 80 60 40 20 0 ppm

22.1

2

69.2

6

76.6

8

77.0

0

77.3

2

129.2

1

130.0

4

132.0

0

132.2

0

201.3

7


120

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

1.4

42

1.4

60

3.7

06

5.0

93

5.1

11

5.1

28

5.1

46

7.2

79

7.3

73

7.3

93

7.4

13

7.7

37

7.7

56

7.8

29

7.8

49

8.0

67

3.2

23

0.8

92

1.0

30

1.0

22

1.0

00

1.0

32

1.0

02


121

220 200 180 160 140 120 100 80 60 40 20 0 ppm

22.0

3

69.4

1

76.6

8

77.0

0

77.3

2

123.1

7

127.0

6

130.3

8

131.5

4

135.1

0

136.7

4

201.1

4


122

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

01

1.4

38

1.4

56

5.0

98

5.1

15

5.1

33

5.1

51

7.2

80

7.4

76

7.4

97

7.8

69

7.8

90

3.1

45

1.0

24

2.0

00

2.0

13


123

220 200 180 160 140 120 100 80 60 40 20 0 ppm

22.1

3

69.2

6

76.6

8

77.0

0

77.3

2

129.2

0

129.9

8

131.5

9

140.4

5

201.1

6


124

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

1.4

45

1.4

62

5.0

98

5.1

15

5.1

33

5.1

50

7.2

78

7.4

38

7.4

58

7.4

78

7.5

85

7.6

04

7.7

87

7.8

06

7.9

11

3.1

21

1.0

21

1.0

19

1.0

00

1.0

19

1.0

07


125

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

22.0

4

69.4

5

76.6

8

77.0

0

77.3

2

126.6

3

128.6

2

130.1

6

133.8

4

134.9

0

135.2

2

201.2

3


126

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

1.4

52

1.4

69

3.6

87

5.1

01

5.1

18

5.1

36

5.1

53

7.2

76

7.3

12

7.3

29

7.3

49

7.4

74

7.4

93

7.5

08

7.5

27

7.6

21

7.6

44

7.6

97

7.7

16

3.2

06

0.8

14

1.0

17

1.0

00

1.0

16

1.0

22

1.0

01


127

220 200 180 160 140 120 100 80 60 40 20 0 ppm

22.0

8

69.5

0

76.6

8

77.0

0

77.3

2

115.2

8

115.5

0

120.9

0

121.1

1

124.3

1

124.3

4

130.5

4

130.6

2

135.3

3

135.3

9

161.5

7

164.0

4

201.2

4


128

9 8 7 6 5 4 3 2 1 0 ppm

-0.0

00

1.4

28

1.4

45

3.8

99

5.0

72

5.0

89

5.1

07

5.1

32

7.0

25

7.0

47

7.2

53

7.3

43

7.3

60

7.3

78

7.3

96

7.4

15

7.4

34

7.8

98

7.9

19

3.0

90

0.8

46

1.0

36

2.0

19

2.0

00

5.1

17

2.0

00


129

220 200 180 160 140 120 100 80 60 40 20 0 ppm

22.5

8

68.8

4

70.1

9

76.6

8

77.0

0

77.3

2

114.8

6

126.1

8

127.4

3

128.3

0

128.6

9

130.9

9

135.8

7

163.2

5

200.6

1


130

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

1.4

41

1.4

58

5.0

86

5.1

03

5.1

20

5.1

37

5.2

05

7.0

63

7.0

84

7.2

67

7.4

57

7.4

76

7.5

08

7.5

27

7.5

46

7.5

66

7.5

95

7.6

14

7.6

37

7.6

56

7.6

75

7.7

61

7.7

79

7.9

28

7.9

49

2.9

59

1.0

08

2.0

13

2.0

00

1.0

73

6.6

28

1.1

46

2.0

02


131

220 200 180 160 140 120 100 80 60 40 20 0 ppm

22.5

2

68.8

0

69.6

5

76.6

8

77.0

0

77.3

2

111.0

7

114.8

1

118.5

7

126.2

5

127.6

5

127.6

8

129.0

4

129.9

2

131.0

0

132.8

4

133.6

9

136.4

3

138.0

2

144.7

2

163.0

5

200.5

6


132

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

1.4

40

1.4

58

5.0

84

5.1

01

5.1

19

5.1

36

5.2

63

7.0

41

7.0

63

7.2

66

7.6

12

7.6

33

7.9

33

7.9

55

8.2

65

8.2

87

3.0

01

1.0

15

2.0

41

2.0

37

2.1

92

2.0

00

2.0

44


133

220 200 180 160 140 120 100 80 60 40 20 0 ppm

22.4

4

68.6

8

68.8

5

76.6

8

77.0

0

77.3

2

114.7

6

123.8

4

126.6

9

127.5

9

131.0

4

143.2

6

147.6

2

162.4

2

200.5

5


134

10 9 8 7 6 5 4 3 2 1 ppm

0.0

00

1.4

64

1.4

82

3.8

43

3.8

58

5.1

47

5.1

63

5.1

79

5.1

96

7.2

76

7.3

71

7.3

93

7.5

08

7.5

27

7.5

47

7.6

45

7.6

64

7.6

82

8.0

15

8.0

37

8.1

95

8.2

13

3.0

91

0.9

84

1.0

23

2.0

18

2.0

30

1.0

00

2.0

22

2.0

15


135

220 200 180 160 140 120 100 80 60 40 20 0 ppm

22.2

7

69.2

6

76.6

8

77.0

0

77.3

2

122.2

7

128.6

8

128.8

1

130.2

3

130.3

4

130.8

1

134.0

1

155.2

5

164.4

6

201.0

9


136

10 9 8 7 6 5 4 3 2 1 ppm

-0.0

00

1.4

74

1.4

91

3.7

36

5.1

42

5.1

59

5.1

77

5.1

94

7.2

15

7.2

37

7.2

41

7.2

63

7.2

87

7.3

06

7.3

25

7.3

94

7.4

16

7.6

16

7.6

20

7.6

28

7.6

34

7.6

36

7.6

50

7.6

59

7.6

67

7.6

71

8.0

23

8.0

45

8.0

92

8.0

96

8.1

11

8.1

14

8.1

29

8.1

33

3.0

12

0.7

73

1.0

04

1.1

60

1.0

63

2.0

17

1.0

00

2.0

29

1.0

51


137

220 200 180 160 140 120 100 80 60 40 20 0 ppm

22.2

6

69.2

8

76.6

8

77.0

0

77.3

2

117.2

0

117.3

3

117.4

2

122.2

5

124.2

4

124.2

8

130.3

5

130.9

6

132.5

4

135.6

6

135.7

5

154.8

5

161.0

6

161.9

9

162.0

3

163.6

6

201.1

0


138

10 9 8 7 6 5 4 3 2 1 0 ppm

-0.0

00

0.9

11

0.9

28

0.9

46

1.4

05

1.4

25

1.4

31

1.4

49

1.4

69

1.4

75

1.4

88

1.5

18

1.5

38

1.5

57

1.5

83

1.8

02

1.8

10

1.8

29

1.8

55

3.7

11

5.0

18

5.0

24

5.0

34

5.0

41

7.0

14

7.0

36

7.0

85

7.1

05

7.2

13

7.2

32

7.2

51

7.2

63

7.4

01

7.4

20

7.4

40

7.8

91

7.9

13

3.1

52

1.2

38

2.1

54

1.0

92

0.8

24

1.0

00

2.0

76

2.0

05

1.0

80

2.0

26

2.0

40


139

220 200 180 160 140 120 100 80 60 40 20 0 ppm

13.8

2

18.2

4

38.2

2

72.6

1

76.6

8

77.0

0

77.3

2

117.2

6

120.4

2

124.9

4

127.9

0

130.1

2

130.8

5

155.0

1

162.7

6

200.5

1


140

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

01

0.9

03

0.9

22

0.9

40

1.5

30

1.5

48

1.5

66

1.5

83

1.6

01

1.6

19

1.6

37

1.8

71

1.8

81

1.8

90

1.9

00

1.9

09

1.9

18

1.9

26

1.9

35

1.9

44

1.9

54

3.7

11

4.9

62

4.9

71

4.9

78

4.9

87

7.1

83

7.2

04

7.2

65

7.4

18

7.4

25

7.4

33

7.5

19

7.5

25

7.5

30

7.5

33

7.5

42

7.7

56

7.7

77

3.0

97

1.0

67

1.1

04

0.8

84

1.0

04

2.0

44

3.0

31

2.0

00

2.0

23


141

220 200 180 160 140 120 100 80 60 40 20 0 ppm

8.8

2

28.9

1

73.7

0

76.6

8

77.0

0

77.3

2

126.8

9

128.9

6

129.1

5

129.7

6

130.5

1

131.0

9

134.3

8

146.6

6

200.8

5


142

9 8 7 6 5 4 3 2 1 0 ppm

-0.0

00

0.9

71

0.9

90

1.0

08

1.6

85

1.7

03

1.7

21

1.7

38

1.7

56

1.7

74

1.7

92

1.9

70

1.9

80

1.9

88

1.9

98

2.0

07

2.0

17

2.0

24

2.0

34

2.0

42

2.0

52

2.0

61

2.0

71

3.5

54

4.8

59

4.8

69

4.8

76

4.8

86

7.1

76

7.1

85

7.1

87

7.1

97

7.2

75

7.7

30

7.7

32

7.7

42

7.7

44

7.7

64

7.7

66

7.7

73

7.7

75

3.1

42

1.2

07

1.0

83

0.8

70

1.0

11

1.0

12

1.0

00

1.0

00


143

220 200 180 160 140 120 100 80 60 40 20 0 ppm

8.9

0

29.8

0

74.8

1

76.6

8

77.0

0

77.3

2

128.3

1

132.8

6

134.6

5

139.8

6

194.4

8


144

9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

0.9

57

0.9

76

0.9

94

1.6

77

1.6

95

1.7

13

1.7

31

1.7

48

1.7

67

1.9

39

1.9

48

1.9

57

1.9

67

1.9

76

1.9

85

1.9

93

2.0

02

2.0

11

2.0

21

2.0

29

2.0

39

2.5

64

4.7

97

4.8

06

4.8

14

4.8

24

6.8

45

6.8

54

7.2

75

7.5

77

7.5

87

3.0

47

1.0

42

1.0

53

3.0

63

1.0

00

1.0

13

1.0

11


145

220 200 180 160 140 120 100 80 60 40 20 0 ppm

8.9

0

15.9

8

29.9

7

74.4

2

76.6

8

77.0

0

77.3

2

127.0

2

133.5

2

137.5

8

150.9

6

193.9

0


146

9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

0.9

65

0.9

83

1.0

02

1.6

60

1.6

78

1.6

96

1.7

14

1.7

32

1.7

50

1.7

68

1.9

30

1.9

40

1.9

49

1.9

59

1.9

67

1.9

77

1.9

84

1.9

94

2.0

02

2.0

13

2.0

21

2.0

31

3.4

38

4.7

63

4.7

73

4.7

81

4.7

90

7.1

45

7.1

55

7.2

77

7.5

08

7.5

18

3.2

59

1.1

95

1.1

72

0.9

18

1.0

00

1.0

17

1.0

11


147

220 200 180 160 140 120 100 80 60 40 20 0 ppm

8.9

1

29.7

0

74.6

7

76.6

8

77.0

0

77.3

2

123.9

4

131.3

9

133.1

1

141.3

1

193.4

2


148

9 8 7 6 5 4 3 2 1 0 ppm

-0.0

00

0.9

57

0.9

76

0.9

94

1.6

49

1.6

67

1.6

85

1.7

02

1.7

20

1.7

38

1.7

56

1.9

22

1.9

32

1.9

41

1.9

51

1.9

59

1.9

69

1.9

76

1.9

86

1.9

95

2.0

05

2.0

13

2.0

23

2.4

23

3.5

45

4.7

40

4.7

50

4.7

58

4.7

68

6.2

15

6.2

24

7.2

22

7.2

31

7.2

87

3.1

94

1.1

37

1.1

53

3.1

72

0.8

72

1.0

08

1.0

02

1.0

00


149

220 200 180 160 140 120 100 80 60 40 20 0 ppm

8.8

8

14.0

6

29.0

0

73.9

1

76.6

8

77.0

0

77.3

2

109.2

9

120.8

6

148.9

2

158.6

7

189.5

5


150

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

01

0.9

69

0.9

88

1.0

06

1.6

56

1.6

74

1.6

92

1.7

27

1.7

45

1.7

64

1.9

39

1.9

58

1.9

67

1.9

76

1.9

86

1.9

93

2.0

03

2.0

11

2.0

21

2.0

39

3.2

56

3.8

49

4.7

65

4.7

74

4.7

82

4.7

91

7.3

23

7.3

31

7.3

48

7.7

31

8.2

99

8.3

07

8.3

20

3.0

37

1.0

42

1.1

03

1.1

99

3.0

42

0.9

87

3.1

73

1.0

55

1.0

01


151

220 200 180 160 140 120 100 80 60 40 20 0 ppm

9.0

3

30.3

3

33.6

5

74.3

6

76.6

8

77.0

0

77.3

2

109.8

4

112.3

9

122.3

0

122.9

3

123.6

5

126.3

0

135.5

8

137.2

6

195.9

0


152

10 9 8 7 6 5 4 3 2 1 0 ppm

0.0

00

0.9

28

0.9

47

0.9

65

1.6

47

1.6

64

1.6

82

1.7

00

1.7

18

1.7

35

1.9

09

1.9

17

1.9

27

1.9

36

1.9

46

1.9

52

1.9

63

1.9

71

1.9

81

3.6

92

3.7

06

4.7

32

4.7

42

7.2

59

7.4

27

7.4

37

7.4

45

7.4

52

7.4

60

7.4

70

7.5

77

7.5

96

7.6

15

7.6

90

7.7

09

7.7

27

7.7

60

7.7

78

8.0

03

8.2

12

8.2

22

8.2

29

8.2

37

8.2

45

8.2

54

8.3

07

8.3

16

8.3

24

8.3

31

8.3

39

8.3

48

3.0

13

1.2

08

1.0

53

0.9

58

1.0

00

2.1

26

2.1

62

1.1

14

2.0

81

1.0

27

1.0

25

1.0

40

7.67.88.08.28.4 ppm

7.427

7.437

7.445

7.452

7.460

7.470

7.577

7.596

7.615

7.690

7.709

7.727

7.760

7.778

8.003

8.212

8.222

8.229

8.237

8.245

8.254

8.307

8.316

8.324

8.331

8.339

8.348

2.126

2.162

1.114

2.081

1.027

1.025

1.040


153

220 200 180 160 140 120 100 80 60 40 20 0 ppm

8.8

3

29.7

6

74.9

3

76.6

8

77.0

0

77.3

2

115.8

6

117.2

3

122.3

2

125.5

2

126.2

3

127.3

6

129.0

2

129.5

3

132.9

8

133.1

7

133.3

9

136.2

8

168.4

1

197.5

3


154

9 8 7 6 5 4 3 2 1 0 ppm

-0.0

00

0.9

28

0.9

47

0.9

65

1.6

26

1.6

44

1.6

62

1.6

79

1.6

97

1.7

15

1.7

33

1.8

90

1.9

01

1.9

09

1.9

19

1.9

27

1.9

38

1.9

44

1.9

55

1.9

62

1.9

73

1.9

81

1.9

92

3.6

86

3.9

17

4.6

89

4.6

99

4.7

05

4.7

15

7.0

26

7.0

32

7.0

48

7.0

55

7.2

66

7.5

72

7.5

90

7.6

10

7.6

82

7.7

01

7.7

19

7.7

49

7.7

67

7.8

16

7.8

22

7.9

47

8.1

16

8.1

39

3.0

06

1.1

46

1.1

45

0.9

43

3.0

49

1.0

07

1.0

94

2.1

33

1.1

26

2.0

36

1.0

46

1.0

38

1.0

00

7.07.27.47.67.88.08.2 ppm

7.026

7.032

7.048

7.055

7.266

7.572

7.590

7.610

7.682

7.701

7.719

7.749

7.767

7.816

7.822

7.947

8.116

8.139

1.094

2.133

1.126

2.036

1.046

1.038

1.000


155

220 200 180 160 140 120 100 80 60 40 20 0 ppm

8.8

5

29.8

9

55.6

7

74.8

1

76.6

8

77.0

0

77.3

2

104.1

2

115.5

2

116.6

9

116.9

2

128.5

2

128.9

7

129.4

6

130.7

4

132.9

5

133.0

5

133.6

9

157.8

7

168.1

9

197.6

0

Iodine promoted α- hydroxylation of ketones Supplementary Information Iodine promoted α-...

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