Supporting InformationS1 Supporting Information Cobalt-Catalyzed C2α-acyloxylation of 2-Substituted...

S1

Supporting Information

Cobalt-Catalyzed C2α-acyloxylation

of 2-Substituted Indoles with tert-Butyl Peresters

Yuxiang Zhou, Chenglong Li, Xiaoyan Yuan, Feiyan Zhang, Xiaozu Liu,* and Peijun Liu*

Generic Drug Research Center of Guizhou Province, Green Pharmaceuticals Engineering Research Center of Guizhou Province, School of Pharmacy, Zunyi

Medical University, Zunyi 563006, P. R. China

*E-mail: [email protected]

*E-mail: [email protected]

Table of Contents

1. General information ............................................................................ S2

2. Preparation of starting materials ........................................................................... S2

3. General procedure for the Co(II)-catalyzed C2α-acyloxylation ........ S2

4. Characterization data of products ......................................................................... S3

5. Gram-scale synthesis and synthetic applications ............................. S17

6. Radical trapping experiments ........................................................... S19

7. References ......................................................................................... S19

8. Single crystal data of product 3aa .................................................. S21

9. Single crystal data of product 3ga .................................................. S27

10. NMR spectra of products ................................................................ S33

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2019

S2

1. General information

Unless otherwise noted, all commercial materials and solvents were used without

further purification. Commercially available chemicals were obtained from Energy

Chemical, TCI, Alfa Aesar and J&K. Thin layer chromatography (TLC) was carried

out on GF254 plates (0.25 mm layer thickness) and visualized under UV light (254

nm). The silica gel (200-300 meshes) was used for column chromatography. 1H and 13C NMR spectra were recorded on Agilent 400 MHz spectrometer using TMS as

internal standard. Spin multiplicities are given as s (singlet), d (doublet), t (triplet), q

(quartet), m (multiplet), dd (doublet of doublet), td (triplet of doublet), as well as brs

(broad). Coupling constants (J) are given in hertz (Hz). High resolution mass spectra

were obtained on Agilent 6210 ESI/TOF spectrometer.

2. Preparation of starting materials

(1) N-Pyrimidinyl-2-methyl indoles 1a-f, N-pyrimidinyl-2,3-dimethyl indole 1g,

9-(pyrimidin-2-yl)-2,3,4,9-tetrahydro-1H-carbazole 1x, and 1-(5-bromopyrimidin

-2-yl)-2-ethyl-1H-indole 1y were prepared according to literature procesure.1

(2) N-Pyrimidinyl-2,3-disubstituted indoles 1h-v were prepared via a modified

Fischer indole synthesis2 followed by protection for the indole -NH.1

(3) 1-(5-Bromopyrimidin-2-yl)-2-methyl-3-propyl-1H-indole-5-carbonitrile 1w was

prepared via a Fischer indole synthesis3 followed by protection for the indole

-NH.1

(4) All the tert-butyl peresters were prepared according to literature procedure.4

3. General procedure for the Co(II)-catalyzed C2α-acyloxylation

To a 25 mL of Schlenk tube equipped with a Teflon-coated magnetic stir bar were

added indole 1 (0.5 mmol, 1.0 equiv), perester 2 (1.5 mmol, 3.0 equiv), Co(acac)2

(0.05 mmol, 10 mol%), and toluene (3 mL). The resulting mixture was stirred at 80 oC

for 1.5 to 24 hours. Upon completion of the reaction as monitored by TLC, the

reaction mixture was then cooled to room temperature, and concentrated under

reduced pressure. The crude residue was purified by flash column chromatography on

silic

3.

4.

(1-(

Foll

76%

= 8.

7.41

6.86

135

62.0

(1-(

N

Foll

60%

1H)

(t, J

(s, 2

132

HRM

(1-(

ca gel (petro

Characte

(Pyrimidin-

N

N N

OBz

3aa

lowing the g

%). mp 132-

.4 Hz, 1H),

1 (t, J = 8.0

6 (s, 1H), 5

.1, 132.9,

0; HRMS (E

(5-Methylp

N

N N

Me

OBz

3ba

lowing the g

%). mp 105-

), 7.97 (d, J

J = 8.0 Hz, 2

2H), 2.27 (s

2.9, 130.2, 1

MS (ESI/[M

(5-Fluoropy

oleum ether

erization d

-2-yl)-1H-in

general pro

-134 oC; 1H

7.98 (d, J =

Hz, 2H), 7.

.97 (s, 2H);

130.1, 129.

ESI/[M + N

yrimidin-2

general pro

-107 oC; 1H

J = 8.4 Hz, 2

2H), 7.32 (t

s, 3H); 13C N

29.6, 128.7

M + Na]+) c

yrimidin-2-

r/ethyl acet

data of pr

ndol-2-yl)m

ocedure, pro

H NMR (400

= 8.3 Hz, 2H

.36 – 7.32 (

; 13C NMR

.5, 128.9, 1

Na]+) calcd f

2-yl)-1H-ind

cedure, pro

NMR (400

2H), 7.61 (d

t, J = 7.8 Hz

NMR (101 M

7, 128.3, 126

alcd for C21

-yl)-1H-ind

S3

tate = 30/1

roducts

methyl benz

oduct 3aa w

0 MHz, CD

H), 7.62 (d,

(m, 1H), 7.2

(101 MHz,

128.3, 123.8

for C20H15O

dol-2-yl)me

oduct 3ba w

0 MHz, CDC

d, J = 7.8 H

z, 1H), 7.23

MHz, CDC

6.2, 123.7,

1H17O2N3Na

dol-2-yl)me

as eluent) t

zoate (3aa)

was obtained

Cl3) δ 8.72

J = 8.0 Hz

27 – 7.23 (m

CDCl3) δ

8, 122.2, 1

O2N3Na+: 35

ethyl benzo

was obtained

Cl3) δ 8.54 (

Hz, 1H), 7.5

3 (t, J = 7.4

Cl3) δ 166.1,

121.9, 120.

a+: 366.121

ethyl benzo

to give the

d as a white

(d, J = 4.8,

, 1H), 7.56

m, 1H), 7.06

166.2, 158.

20.5, 116.8

2.1056, fou

oate (3ba)

d as a white

(s, 2H), 8.4

53 (t, J = 8.0

Hz, 1H), 6.

158.0, 156

5, 114.6, 10

3, found 36

ate (3ca)

desired pro

e solid (125

, 2H), 8.57

– 7.52 (m,

6 (t, J = 4.8,

1, 158.0, 13

8, 115.1, 10

und 352.105

e solid (103

6 (d, J = 8.4

0 Hz, 1H),

84 (s, 1H),

6.3, 137.0, 1

08.1, 61.7, 1

66.1214.

oduct

mg,

(d, J

1H),

1H),

37.1,

08.7,

59.

mg,

4 Hz,

7.40

5.94

35.1,

15.0;

S4

Following the general procedure, product 3ca was obtained as a white solid (107 mg,

62%). mp 112-114 oC; 1H NMR (400 MHz, CDCl3) δ 8.57 (s, 2H), 8.44 (d, J = 8.4 Hz,

1H), 7.97 (d, J = 8.3 Hz, 2H), 7.62 (d, J = 7.7 Hz, 1H), 7.55 (t, J = 7.6 Hz, 1H), 7.41

(t, J = 7.6 Hz, 2H), 7.34 (t, J = 7.8 Hz, 1H), 7.27 – 7.23 (m, 1H), 6.86 (s, 1H), 5.91 (s,

2H); 13C NMR (101 MHz, CDCl3) δ 166.1, 154.7 (d, J = 260.4 Hz), 154.2 (d, J = 2.9

Hz), 145.8 (d, J = 21.9 Hz), 137.1 , 135.1, 133.1, 130.0, 129.6, 128.7, 128.4, 124.0,

122.4, 120.7, 114.6, 109.0, 61.6; HRMS (ESI/[M + Na]+) calcd for C20H14O2N3FNa+:

370.0962, found 370.0965.

(1-(5-Bromopyrimidin-2-yl)-1H-indol-2-yl)methyl benzoate (3da)

Following the general procedure, product 3da was obtained as a white solid (147 mg,


1H), 8.00 (d, J = 8.0 Hz, 2H), 7.61 – 7.54 (m, 2H), 7.42 (t, J = 7.6 Hz, 2H), 7.34 (t, J

= 7.8 Hz, 1H), 7.27 – 7.24 (m, 1H), 6.86 (s, 1H), 5.91 (s, 2H); 13C NMR (101 MHz,

CDCl3) δ 166.1, 158.5, 156.3, 137.0, 135.3, 133.1, 130.0, 129.6, 129.0, 128.4, 124.1,

122.6, 120.7, 115.3, 114.2, 109.5, 61.8; HRMS (ESI/[M + Na]+) calcd for

C20H14O2N3BrNa+: 430.0162, found 430.0164.

(5-Methyl-1-(pyrimidin-2-yl)-1H-indol-2-yl)methyl benzoate (3ea)

Following the general procedure, product 3ea was obtained as a colorless oil (95 mg,

55%). 1H NMR (400 MHz, CDCl3) δ 8.70 (d, J = 4.8, 2H), 8.46 (d, J = 8.6, Hz, 1H),

7.98

1H)

MH

128

C21H

(5-C

Cl

Foll

74%

(d, J

2H)

NM

129

calc

(3-M

Foll

44%

= 8.

1H)

NM

129

Na]

(1-(

8 (d, J = 8.0

), 7.04 (d, J

Hz, CDCl3)

.3, 125.3, 1

H17O2N3Na

Chloro-1-(p

N

N N

O

3fa

lowing the

%). mp 139-

J = 8.8 Hz,

), 7.26 (d, J

MR (101 MH

9.6, 128.4, 1

cd for C20H1

Methyl-1-(p

N

Me

N N

OBz

3ga

lowing the

%). mp 91-9

.2 Hz, 1H),

), 7.38 – 7.

MR (101 MH

9.4, 128.2, 1+) calcd for

(5-Bromopy

0 Hz, 2H), 7

J = 4.8, 1H

δ 166.2, 15

20.4, 116.5

a+: 366.1213

pyrimidin-2

OBz

general pro

-141 oC; 1H

1H), 7.99 (

J = 8.4 Hz,

Hz, CDCl3)

27.72 , 123

14O2N3ClNa

pyrimidin-2

general pro

92 oC; 1H NM

7.82 (d, J =

26 (m, 4H)

Hz, CDCl3)

124.5, 121.8

r C21H17O2N

yrimidin-2-

7.54 (t, J = 8

H), 6.78 (s,

58.2, 157.9,

5, 114.9, 108

3, found 366

2-yl)-1H-in

ocedure, pro

H NMR (400

(d, J = 8.0 H

1H), 7.10 (t

) δ 166.1, 1

3.9, 119.9, 1

a+: 386.0667

2-yl)-1H-in

ocedure, pro

MR (400 M

= 7.4 Hz, 2

), 7.02 (t, J

) δ 166.3, 1

8, 119.0, 1

N3Na+: 366.

-yl)-3-ethyl

S5

8.0 Hz, 1H)

1H), 5.95 (

135.4, 135

8.5, 62.1, 2

6.1216.

ndol-2-yl)m

oduct 3fa w

0 MHz, CD

Hz, 2H), 7.5

t, J = 4.8 H

158.1, 157.

117.1, 116.4

7, found 38

ndol-2-yl)m

oduct 3ga w

MHz, CDCl3

2H), 7.62 (d

J = 3.8 Hz,

158.1, 158.

18.2, 116.7

1213, found

l-1H-indol-

), 7.42 – 7.3

(s, 2H), 2.4

5.3, 132.9, 1

1.3; HRMS

methyl benzo

was obtained

DCl3) δ 8.73

57 – 7.53 (m

Hz, 1H), 6.78

9, 136.9, 1

4, 107.6, 61

86.0670.

methyl benz

was obtaine

3) δ 8.69 (d,

d, J = 7.7 Hz

1H), 5.99

0, 136.5, 1

7, 114.4, 58

d 366.1216.

-2-yl)methy

8 (m, 3H),

45 (s, 3H);

131.6, 130.2

(ESI/[M +

oate (3fa)

d as a white

3 (d, J = 4.8

m, 2H), 7.42

8 (s, 1H), 5

35.4, 133.1

.9; HRMS (

oate (3ga)

d as a whit

J = 4.4 Hz,

z, 1H), 7.47

(s, 2H), 2.4

32.7, 130.2

.4, 8.9; HR

.

yl benzoate

7.15 (d, 8.613C NMR

2, 129.6, 12

+ Na]+) calcd

e solid (134

8 Hz, 2H),

2 (t, J = 7.6

.95 (s, 2H);

1, 130.1, 13

(ESI/[M + N

te solid (76

, 2H), 8.44

7 (t, J = 7.3

47 (s, 3H);

2, 129.9, 12

RMS (ESI/[

e (3ha)

6 Hz,

(101

29.1,

d for

mg,

8.52

6 Hz,

; 13C

30.0,

Na]+)

mg,

(d, J

3 Hz,

; 13C

29.7,

M +

S6

Following the general procedure, product 3ha was obtained as a white solid (135 mg,


1H), 7.85 (d, J = 8.5 Hz, 2H), 7.65 (d, J = 8.1 Hz, 1H), 7.52 – 7.48 (m, 1H), 7.38 –

7.33 (m, 3H), 7.29 (d, J = 7.4 Hz, 1H), 5.91 (s, 2H), 2.93 (q, J = 7.5 Hz, 2H), 1.33 (t,

J = 7.6 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 166.3, 158.4, 156.3, 136.59 , 132.9,

130.1, 129.4, 129.3, 128.9, 128.3, 125.6, 124.7, 122.2, 119.2, 114.8, 114.1, 58.0, 17.5,

15.7; HRMS (ESI/[M + H]+) calcd for C22H19O2N3Br+: 436.0655, found 436.0658.

(1-(5-Bromopyrimidin-2-yl)-3-isopropyl-1H-indol-2-yl)methyl benzoate (3ia)

Following the general procedure, product 3ia was obtained as a white solid (126 mg,


1H), 7.88 – 7.83 (m, 3H), 7.51 (t, J = 7.3 Hz, 1H), 7.38 – 7.32 (m, 3H), 7.27 – 7.23 (m,

1H), 5.92 (s, 2H), 3.51 – 3.44 (m, 1H), 1.54 (d, J = 7.1 Hz, 6H); 13C NMR (101 MHz,

CDCl3) δ 166.2, 158.5, 156.2, 136.9, 132.9, 130.1, 129.4, 129.0, 128.4, 128.2, 127.7,

124.2, 121.7, 120.8, 114.5, 114.4, 57.8, 26.2, 22.8; HRMS (ESI/[M + H]+) calcd for

C23H21O2N3Br+: 450.0812, found 450.0811.

(3-Propyl-1-(pyrimidin-2-yl)-1H-indol-2-yl)methyl benzoate (3ja)

Following the general procedure, product 3ja was obtained as a white solid (130 mg,

70%). mp 58-60 oC; 1H NMR (400 MHz, CDCl3) δ 8.68 (d, J = 4.8 Hz, 2H), 8.43 (d, J

= 8.3 Hz, 1H), 7.80 (d, J = 7.8 Hz, 2H), 7.65 (d, J = 7.8 Hz, 1H), 7.47 (t, J = 7.4 Hz,

S7

1H), 7.37 – 7.24 (m, 4 H), 7.01 (t, J = 4.8 Hz, 1H), 5.95 (s, 2H), 2.89 (t, J = 7.5 Hz,

2H), 1.80 – 1.71 (m, 2H), 1.02 (t, J = 7.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ

166.3, 158.1, 158.0, 136.7, 132.7, 130.2, 129.9, 129.4, 129.2, 128.2, 124.3, 122.9,

121.7, 119.2, 116.7, 114.5, 58.3, 26.2, 24.0, 14.1; HRMS (ESI/[M + Na]+) calcd for

C23H21O2N3Na+: 394.1526, found 394.1529.

(3-Isobutyl-1-(pyrimidin-2-yl)-1H-indol-2-yl)methyl benzoate (3ka)

Following the general procedure, product 3ka was obtained as a white solid (116 mg,

60%). mp 114-116 oC; 1H NMR (400 MHz, CDCl3) δ 8.68 (d, J = 4.8 Hz, 2H), 8.42

(d, J = 8.4 Hz, 1H), 7.78 (d, J = 7.5 Hz, 2H), 7.63 (d, J = 7.8 Hz, 1H), 7.46 (t, J = 7.4

Hz, 1H), 7.36 – 7.23 (m, 4H), 7.01 (t, J = 4.8 Hz, 1H), 5.94 (s, 2H), 2.77 (d, J = 7.3

Hz, 2H), 2.10 – 2.00 (m, 1H), 1.01 (d, J = 6.6 Hz, 6H); 13C NMR (101 MHz, CDCl3)

δ 166.3, 158.1, 158.0, 136.6, 132.7, 130.2, 130.1, 129.4, 129.4, 128.2, 124.3, 122.0,


C24H23O2N3Na+: 408.1682, found 408.1685.

(3-Benzyl-1-(5-bromopyrimidin-2-yl)-1H-indol-2-yl)methyl benzoate (3la)

Following the general procedure, product 3la was obtained as a white solid (204 mg,


1H), 7.81 (d, J = 8.3 Hz, 2H), 7.59 – 7.45 (m, 2H), 7.39 – 7.28 (m, 5H), 7.25 – 7.12

(m, 4H), 5.95 (s, 2H), 4.30 (s, 2H); 13C NMR (101 MHz, CDCl3) δ 166.2, 158.5,

156.2, 139.9, 136.6, 132.9, 130.8, 130.0, 129.5, 129.2, 128.5, 128.3, 128.2, 126.1,


C27H21BrN3O2+: 498.0812, found 498.0819.

S8

(1-(5-Bromopyrimidin-2-yl)-3-(4-methoxyphenyl)-1H-indol-2-yl)methyl benzoate

(3ma)

Following the general procedure, product 3ma was obtained as a white solid (131 mg,


1H), 7.86 (d, J = 8.0 Hz, 2H), 7.66 (d, J = 7.9 Hz, 1H), 7.53 – 7.49 (m, 3H), 7.42 –

7.34 (m, 3H), 7.28 (t, J = 7.6 Hz, 1H), 7.05 (d, J = 8.5 Hz, 2H), 5.81 (s, 2H), 3.88 (s,

3H); 13C NMR (101 MHz, CDCl3) δ 166.2, 159.2, 158.6, 156.2, 136.4, 132.9, 131.2,

130.1, 129.7, 129.5, 128.8, 128.3, 125.3, 125.2, 125.0, 122.7, 120.2, 114.7, 114.6,

114.2, 59.3, 55.3; HRMS (ESI/[M + Na]+) calcd for C27H20O3N3BrNa+: 536.0580,

found 536.0583.

(5-Chloro-3-(4-methoxyphenyl)-1-(pyrimidin-2-yl)-1H-indol-2-yl)methyl

benzoate (3na)

N

N N

Cl

OMe

OBz

3na

Following the general procedure, product 3na was obtained as a light yellow solid

(120 mg, 51%). mp 138-139 oC; 1H NMR (400 MHz, CDCl3) δ 8.69 (d, J = 4.8 Hz,

2H), 8.42 (d, J = 8.9 Hz, 1H), 7.80 (d, J = 7.8 Hz, 2H), 7.62 (d, J = 2.2 Hz, 1H), 7.50

– 7.47 (m, 3H), 7.35 – 7.31 (m, 3H), 7.06 – 7.04 (m, 3H), 5.84 (s, 2H), 3.88 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 166.1, 159.3, 158.2, 157.8, 134.9, 132.8, 131.2, 130.1,

129.93, 129.4, 128.2, 128.0, 124.8, 124.8, 123.8, 119.5, 117.3, 115.8, 114.4, 59.3,

55.4; HRMS (ESI/[M + Na]+) calcd for C27H20O3N3ClNa+: 492.1085, found

492.1089.

(1-(5-Bromopyrimidin-2-yl)-3-(4-fluorophenyl)-1H-indol-2-yl)methyl benzoate

(3oa)

S9

Following the general procedure, product 3oa was obtained as a white solid (125 mg,


1H), 7.85 (d, J = 8.4 Hz, 2H), 7.62 (d, J = 7.9 Hz, 1H), 7.58 – 7.50 (m, 3H), 7.43 –

7.35 (m, 3H), 7.30 (t, J = 7.5 Hz, 1H), 7.21 (t, J = 8.7 Hz, 2H), 5.80 (s, 2H); 13C NMR

(101 MHz, CDCl3) δ 166.1, 162.4 (d, J = 247.1 Hz), 158.6, 156.1, 136.3, 133.0, 131.7

(d, J = 8.1 Hz), 130.1, 130.0, 129.4, 128.9 (d, J = 3.2 Hz), 128.5, 128.3, 125.1, 124.4,

122.8, 119.9, 115.8 (d, J = 21.5 Hz), 114.8, 114.7, 59.0; HRMS (ESI/[M + Na]+)

calcd for C26H17O2N3BrFNa+: 524.0380, found 524.0382.

(1-(5-Bromopyrimidin-2-yl)-3-(4-chlorophenyl)-1H-indol-2-yl)methyl benzoate

(3pa)

Following the general procedure, product 3pa was obtained as a white solid (133 mg,


1H), 7.84 (d, J = 8.0 Hz, 2H), 7.62 (d, J = 7.9 Hz, 1H), 7.54 – 7.47 (m, 5H), 7.43 –

7.37 (m, 3H), 7.30 (t, J = 7.5 Hz, 1H), 5.79 (s, 2H); 13C NMR (101 MHz, CDCl3) δ

166.0, 158.6, 156.1, 136.4, 133.6, 133.0, 131.4, 131.3, 130.2, 129.9, 129.4, 129.0,

128.3, 128.3, 125.2, 124.2, 122.9, 119.9, 114.9, 114.7, 59.0; HRMS (ESI/[M + H]+)

calcd for C26H18BrClN3 O2+: 518.0265, found 518.0268.

(3-(4-Bromophenyl)-1-(5-bromopyrimidin-2-yl)-1H-indol-2-yl)methyl benzoate

(3qa)

S10

Following the general procedure, product 3qa was obtained as a white solid (145 mg,


1H), 7.83 (d, J = 8.2 Hz, 2H), 7.65 – 7.61 (m, 3H), 7.54 – 7.50 (m, 1H), 7.47 (d, J =

8.2, 2H), 7.43 – 7.35 (m, 3H), 7.30 (t, J = 7.7 Hz, 1H), 5.79 (s, 2H); 13C NMR (101

MHz, CDCl3) δ 166.1, 158.7, 156.1, 136.4, 133.0, 131.9, 131.7, 130.2, 129.9, 129.4,

128.3, 128.2, 125.2, 124.2, 122.9, 121.8, 119.8, 114.9, 114.7, 59.0; HRMS (ESI/[M +

Na]+) calcd for C26H17O2N3Br2Na+: 583.9580, found 583.9583.

(1-(5-Bromopyrimidin-2-yl)-5-methyl-3-propyl-1H-indol-2-yl)methyl benzoate

(3ra)

Following the general procedure, product 3ra was obtained as a white solid (151 mg,


1H), 7.85 (d, J = 8.4 Hz, 2H), 7.52 – 7.48 (m, 1H), 7.41 (s, 1H), 7.35 (t, J = 7.7 Hz,

2H), 7.17 (d, J = 8.6 Hz, 1H), 5.89 (s, 2H), 2.85 (t, J = 7.5 Hz, 2H), 2.49 (s, 3H), 1.78

– 1.69 (m, 2 H), 1.02 (t, J = 7.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 166.4, 158.3,

156.3, 134.8, 132.8, 131.6, 130.2, 129.8, 129.5, 129.4, 128.2, 126.0, 123.7, 119.1,

114.7, 113.7, 58.2, 26.2, 23.9, 21.4, 14.1; HRMS (ESI/[M + Na]+) calcd for

C24H22O2N3BrNa+: 486.0788, found 486.0791.

(1-(5-bromopyrimidin-2-yl)-5-methoxy-3-propyl-1H-indol-2-yl)methyl benzoate

(3sa)

S11

Following the general procedure, product 3sa was obtained as a white solid (139 mg,


1H), 7.86 (d, J = 7.8 Hz, 2H), 7.50 (t, J = 7.3 Hz, 1H), 7.35 (t, J = 7.6 Hz, 2H), 7.06 (s,

1H), 6.98 (d, J = 9.1 Hz, 1H), 5.88 (s, 2H), 3.90 (s, 3H), 2.84 (t, J = 7.4 Hz, 2H), 1.78

– 1.69 (m, 2H), 1.02 (t, J = 7.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 166.4, 158.3,

156.2, 155.6, 132.8, 131.4, 130.5, 130.2, 130.1, 129.4, 128.3, 123.7, 116.0, 113.6,


C24H22O3N3BrNa+: 502.0737, found 502.0739.

(1-(5-Bromopyrimidin-2-yl)-5-fluoro-3-propyl-1H-indol-2-yl)methyl benzoate

(3ta)

Following the general procedure, product 3ta was obtained as a white solid (187 mg,

80%). mp 120-122 oC; 1H NMR (400 MHz, CDCl3) δ 8.68 (s, 2H), 8.38 (ddd, J = 9.1,

4.6, 1.0 Hz, 1H), 7.84 (d, J = 8.4 Hz, 2H), 7.50 (td, J = 7.4, 1.4 Hz, 1H), 7.35 (t, J =

8.4 Hz, 2H), 7.28 – 7.25 (m, 1H), 7.10 – 7.04 (m, 1H), 5.88 (s, 2H), 2.83 (t, J = 7.5

Hz, 2H), 1.76 – 1.67 (m, 2H), 1.01 (t, J = 7.4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ

166.3, 158.9 (d, J = 238.9 Hz), 158.4, 156.0, 132.9, 132.8, 131.4, 130.2 (d, J = 9.5

Hz), 130.0, 129.4, 128.3, 123.5 (d, J = 4.2 Hz), 116.0 (d, J = 8.8 Hz), 114.2, 112.4 (d,

J = 25.0 Hz), 104.6 (d, J = 23.4 Hz), 58.1, 26.1, 23.8, 14.0; HRMS (ESI/[M + Na]+)

calcd for C23H19O2N3BrFNa+: 490.0537, found 490.0540.

(1-(5-Bromopyrimidin-2-yl)-5-chloro-3-propyl-1H-indol-2-yl)methyl benzoate

(3ua)

S12

N

Cl

N N

Br

OBz

3ua

Following the general procedure, product 3ua was obtained as a white solid (196 mg,


1H), 7.84 (d, J = 8.3 Hz, 2H), 7.58 (s, 1H), 7.53 – 7.48 (m, 1H), 7.35 (t, J = 7.5 Hz,

2H), 7.30 – 7.27 (m, 1H), 5.87 (s, 2H), 2.83 (t, J = 7.5 Hz, 2H), 1.76 – 1.67 (m, 2H),

1.01 (t, J = 7.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 166.2, 158.4, 156.0, 134.8,

132.9, 131.2, 130.5, 130.0, 129.4, 128.3, 127.7, 124.6, 123.1, 118.8, 116.1, 114.4,

58.0, 26.1, 23.8, 14.0; HRMS (ESI/[M + Na]+) calcd for C23H19O2N3BrClNa+:

506.0241, found 506.0244.

(5-Bromo-1-(5-bromopyrimidin-2-yl)-3-propyl-1H-indol-2-yl)methyl benzoate

(3va)

Following the general procedure, product 3va was obtained as a white solid (166 mg,


1H), 7.84 (d, J = 7.9 Hz, 2H), 7.74 (s, 1H), 7.50 (t, J = 7.3 Hz, 1H), 7.42 (d, J = 8.9

Hz, 1H), 7.35 (t, J = 7.6 Hz, 2H), 5.88 (s, 2H), 2.83 (t, J = 7.5 Hz, 2H), 1.77 – 1.67 (m,

2H), 1.01 (t, J = 7.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 166.2, 158.5, 156.0,

135.2, 132.9, 131.1, 131.1, 130.0, 129.4, 128.3, 127.3, 123.0, 121.9, 116.4, 115.4,

114.5, 57.9, 26.1 , 23.9, 14.09; HRMS (ESI/[M + Na]+) calcd for C23H19O2N3Br2Na+:

549.9736, found 549.9738.

(1-(5-Bromopyrimidin-2-yl)-5-cyano-3-propyl-1H-indol-2-yl)methyl benzoate

(3wa)

S13

Following the general procedure, product 3wa was obtained as a white solid (147 mg,


1H), 7.97 (d, J = 1.8 Hz, 1H), 7.81 (d, J = 7.8 Hz, 2H), 7.57 (dd, J = 8.7, 1.8 Hz,1H),

7.51 (t, J = 7.8 Hz, 1H), 7.35 (t, J = 7.8 Hz, 2H), 5.88 (s, 2H), 2.88 (t, J = 7.5 Hz, 2H),

1.76 – 1.70 (m, 2H), 1.02 (t, J = 7.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 166.1,

158.8, 155.7, 138.2, 133.1, 132.3, 129.7, 129.4, 129.2, 128.3, 127.4, 124.5, 123.2,


C24H19O2N4BrNa+: 497.0584, found 497.0586.

9-(Pyrimidin-2-yl)-2,3,4,9-tetrahydro-1H-carbazol-1-yl benzoate (3xa)

Following the general procedure, product 3xa was obtained as a white solid (83 mg,

45%). mp 148-150 oC; 1H NMR (400 MHz, CDCl3) δ 8.61 (d, J = 8.3 Hz, 1H), 8.54

(d, J = 4.7 Hz, 2H), 7.87 (d, J = 7.9 Hz, 2H), 7.60 (d, J = 7.7 Hz, 1H), 7.46 (t, J = 7.2

Hz, 1H), 7.37 (t, J = 7.7 Hz, 1H), 7.31 (t, J = 7.6 Hz, 2H), 7.27 (d, J = 6.4 Hz, 1H),

7.04 – 7.02 (m, 1H), 6.85 (t, J = 4.7 Hz, 1H), 3.00 (dt, J = 16.5, 4.4 Hz, 1H), 2.80 –

2.72 (m, 1H), 2.36 – 2.30 (m, 1H), 2.24 – 2.17 (m, 1H), 2.12 – 1.98 (m, 2H); 13C

NMR (101 MHz, CDCl3) δ 166.0, 158.1, 157.8, 136.6, 132.5, 132.2, 130.9, 129.4,

128.7, 128.1, 124.5, 121.9, 120.6, 118.7, 116.2, 115.5, 67.1, 30.2, 21.3, 18.5; HRMS

(ESI/[M + Na]+) calcd for C23H19O2N3Na+: 392.1369, found 392.1374.

1-(1-(5-Bromopyrimidin-2-yl)-1H-indol-2-yl)ethyl benzoate (3ya)

S14

Following the general procedure, product 3ya was obtained as a white solid (115 mg,


1H), 7.90 (d, J = 7.8 Hz, 2H), 7.62 (d, J = 7.7 Hz, 1H), 7.52 (t, J = 7.3 Hz, 1H), 7.37

(t, J = 7.6 Hz, 2H), 7.32 (t, J = 7.7 Hz, 1H), 7.25 (t, J = 7.6 Hz, 1H ), 7.02 (q, J = 6.4

Hz, 1H), 6.92 (s, 1H), 1.86 (d, J = 6.4 Hz, 4H); 13C NMR (101 MHz, CDCl3) δ 165.7,

158.5, 156.2, 140.4, 136.9, 132.9, 130.2, 129.4, 128.6, 128.2, 124.0, 122.4, 120.7,

114.7, 114.4, 107.1, 67.3, 19.8; HRMS (ESI/[M + H]+) calcd for C21H17BrN3O2+

422.0499, found 422.0496.

(1-Methyl-1H-indol-2-yl)methyl benzoate (3za)

Following the general procedure, product 3za was obtained as a white solid (72 mg,

54%). mp 94-95 oC; 1H NMR (400 MHz, CDCl3) δ 8.05 (d, J = 8.4 Hz, 2H), 7.63 (d, J

= 7.9 Hz, 1H), 7.56 (t, J = 7.4 Hz, 1H), 7.43 (t, J = 8.1 Hz, 2H), 7.35 (d, J = 8.3 Hz,

1H), 7.29 – 7.25 (m, 1H), 7.13 (t, J = 7.6 Hz, 1H), 6.67 (s, 1H), 5.53 (s, 2H), 3.82 (s,

3H); 13C NMR (101 MHz, CDCl3) δ 166.2, 138.0, 133.6, 133.2, 129.8, 129.7, 128.4,


C17H16 NO2+: 266.1176, found 266.1177.

(1-Acetoxy-1H-indol-2-yl)methyl benzoate (3aaa)

N

OCOMe

OBz

3aaa

Following the general procedure, product 3aaa was obtained as a white solid (86 mg,

56%). mp 41-43 oC; 1H NMR (600 MHz, CDCl3) δ 8.17 (d, J = 8.4 Hz, 1H), 8.11 –

8.08 (m, 2H), 7.61 – 7.56 (m, 1H), 7.54 (dt, J = 7.8, 1.0 Hz, 1H), 7.46 (t, J = 7.8 Hz,

2H), 7.34 (ddd, J = 8.4, 7.1, 1.1 Hz, 1H), 7.28 – 7.24 (m, 1H), 6.76 (s, 1H), 5.71 (s,

2H), 4.03 (s, 3H); 13C NMR (151 MHz, CDCl3) δ 166.1, 152.0, 136.8, 134.8, 133.1,

129.9, 129.7, 128.7, 128.4, 124.9, 123.3, 120.8, 115.6, 110.8, 61.0, 53.9; HRMS

(ESI/[M + H]+) calcd for C18H16NO4+: 310.1074, found 310.1077.

(1-(4-Chlorobenzoyl)-5-methoxy-3-(2-methoxy-2-oxoethyl)-1H-indol-2-yl)methyl

benzoate (7)

S15

N

CO2Me

Cl

MeO

O

OBz

7

Following the general procedure, product 7 was obtained as a light yellow solid (142

mg, 58%). mp 106-108 oC; 1H NMR (400 MHz, CDCl3) δ 7.90 (d, J = 8.3 Hz, 2H),

7.69 (d, J = 8.5 Hz, 2H), 7.51 (t, J = 7.6 Hz, 1H), 7.44 (d, J = 8.5 Hz, 2H), 7.35 (t, J =

7.8 Hz, 2H), 7.03 (s, 1H), 6.75 – 6.74 (m, 2H), 5.65 (s, 2H), 3.92 (s, 2H), 3.84 (s, 3H),

3.65 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 170.9, 168.1, 165.9, 156.0, 139.7, 133.4,

133.2, 133.1, 131.3, 131.3, 129.6, 129.6, 129.2, 128.3, 116.7, 115.1, 113.9, 101.7,

56.9, 55.7, 52.3, 30.1; HRMS (ESI/[M + Na]+) calcd for C27H22O6NClNa+: 514.1028,

found 514.1033.

(1-(5-Bromopyrimidin-2-yl)-1H-indol-2-yl)methyl 4-methoxybenzoate (3db)

Following the general procedure, product 3db was obtained as a light yellow solid

(158 mg, 72%). mp 129-131 oC; 1H NMR (400 MHz, CDCl3) δ 8.71 (s, 2H), 8.51 (d,

J = 8.0 Hz, 1H), 7.97 (d, J = 8.0 Hz, 2H), 7.60 (d, J = 7.7 Hz, 1H), 7.34 (t, J = 7.8 Hz,

1H), 7.28 – 7.24 (m, 1H), 6.91 (d, J = 8.1 Hz, 2H), 6.85 (s, 1H), 5.87 (s, 2H), 3.86 (s,

3H); 13C NMR (101 MHz, CDCl3) δ 165.8, 163.4, 158.4, 156.2, 136.9, 135.5, 131.6,

129.0, 124.0, 122.5, 122.4, 120.6, 115.2, 114.1, 113.6, 109.2, 61.5, 55.4; HRMS

(ESI/[M + H]+) calcd for C21H17O3N3Br+: 438.0448, found 438.0450.

(1-(5-Bromopyrimidin-2-yl)-1H-indol-2-yl)methyl 3-methylbenzoate (3dc)

S16

Following the general procedure, product 3dc was obtained as a white solid (148 mg,


1H), 7.79 (d, J = 8.8 Hz, 1H), 7.78 (s, 1H), 7.60 (d, J = 7.7 Hz, 1H), 7.37 – 7.30 (m,

3H), 7.28 – 7.24 (m, 1H), 6.85 (s, 1H), 5.89 (s, 2H), 2.38 (s, 3H); 13C NMR (101 MHz,

CDCl3) δ 166.3, 158.5, 156.3, 138.2, 137.0, 135.3, 133.8, 130.1, 129.9, 129.0, 128.3,

126.7, 124.1, 122.6, 120.7, 115.2, 114.2, 109.5, 61.7, 21.3; HRMS (ESI/[M + Na]+)

calcd for C21H16O2N3BrNa+: 444.0318, found 444.0321.

(1-(5-Bromopyrimidin-2-yl)-1H-indol-2-yl)methyl 4-chlorobenzoate (3dd)

Following the general procedure, product 3dd was obtained as a white solid (144 mg,



(t, J = 7.8 Hz, 1H), 7.28 – 7.24 (m, 1H), 6.84 (s, 1H), 5.90 (s, 2H); 13C NMR (101

MHz, CDCl3) δ 165.3, 158.5, 156.3, 139.5, 137.0, 134.9, 131.0, 128.9, 128.8, 128.5,


C20H13O2N3BrClNa+: 463.9772, found 463.9773.

(1-(5-Bromopyrimidin-2-yl)-1H-indol-2-yl)methyl 1-naphthoate (3de)

Following the general procedure, product 3de was obtained as a white solid (143 mg,

62%). mp 114-115 oC; 1H NMR (400 MHz, CDCl3) δ 8.92 (d, J = 8.6 Hz, 1H), 8.75 (s,


(d, J = 8.1 Hz, 1H), 7.60 (t, J = 7.9 Hz, 2H), 7.55 – 7.52 (m, 1H), 7.45 (t, J = 7.7 Hz,

1H), 7.35 (t, J = 7.7 Hz, 1H), 7.28 – 7.25 (m, 1H), 6.91 (s, 1H), 5.99 (s, 2H); 13C

NMR (101 MHz, CDCl3) δ 167.0, 158.5, 156.3, 137.0, 135.2, 133.8, 133.5, 131.4,

130.3, 129.0, 128.5, 127.8, 126.8, 126.2, 125.7, 124.5, 124.2, 122.6, 120.7, 115.3,

S17

114.2, 109.9, 61.8; HRMS (ESI/[M + Na]+) calcd for C24H16O2N3BrNa+: 480.0318,

found 480.0320.

(1-(5-Bromopyrimidin-2-yl)-1H-indol-2-yl)methyl acetate (3df)

Following the general procedure, product 3df was obtained as a white solid (56 mg,


1H), 7.58 (d, J = 7.6 Hz, 1H), 7.32 (t, J = 7.5 Hz, 1H), 7.26 – 7.22 (m, 1H), 6.78 (s,

1H), 5.66 (s, 2H), 2.08 (s, 3H); 13C NMR (101 MHz, CDC3) δ 170.6, 158.4, 156.2,

136.9, 135.2, 128.9, 124.1, 122.6, 120.6, 115.3, 114.1, 109.5, 61.3, 21.0; HRMS

(ESI/[M + Na]+) calcd for C15H12O2N3BrNa+: 368.0005, found 368.0009.

5. Gram-scale synthesis and synthetic applications

(1) Gram-scale synthesis

Following the general procedure, to a solution of indole 1d (1.15 g, 4.0 mmol) in

toluene (24 mL) were added perester 2a (2.32 mL, 12.0 mmol) and Co(acac)2 (0.104 g,

0.4 mmol). The resulting mixture was stirred at 80 oC for 3 hours. The reaction

mixture was then cooled to room temperature, and concentrated under reduced

pressure. The crude residue was purified by flash column chromatography on silica

gel (petroleum ether/ethyl acetate = 30/1 as eluent) to give the desired product 3da as

a white solid (0.88 g, 54% yield).

S18

Following the general procedure, to a solution of indole 1g (0.65 g, 2.5 mmol) in


0.25 mmol). The resulting mixture was stirred at 80 oC for 1.5 hours. The reaction



gel (petroleum ether/ethyl acetate = 30/1 as eluent) to give the desired product 3ga as


Following the general procedure, to a solution of indole 1za (1.45 g, 10.0 mmol) in


1.0 mmol). The resulting mixture was stirred at 60 oC for 5 hours. The reaction



gel (petroleum ether/ethyl acetate = 30/1 as eluent) to give the desired product 3za as


(2) Synthetic applications

To a stirred solution of NaOH (12.0 mg, 0.30 mmol) in methanol (1.5 mL) was

added 3da (55.0 mg, 0.13 mmol), and the mixture was stirred for 3 hours at room

temperature (Monitored by TLC). After that, the reaction mixture was concentrated under reduced pressure. The crude residue was purified by flash column chromatography on silica gel (petroleum ether/acetate ethyl = 8/1 as eluent) to give the desired product 4 as a white solid (37.1 mg, 90% yield). mp 122-124 oC; 1H NMR (400 MHz, CDCl3) δ 8.78 (s, 2H), 8.48 (d, J = 8.4 Hz, 1H), 7.58 (d, J = 7.6 Hz, 1H), 7.32 (t, J = 7.8 Hz, 1H), 7.25 (t, J = 7.6 Hz, 1H), 6.71 (s, 1H), 4.76 (s, 2H); 13C NMR (101 MHz, CDCl3) δ 158.7, 155.9, 139.7, 136.8, 129.2, 124.2, 122.9, 120.9, 115.5, 113.7, 110.2, 58.0; HRMS (ESI/ [M+H]+) calcd for C13H11BrN3O

+: 304.0080, found 304.0079.

S19

To a stirred solution of 3za (40.0 mg, 0.15 mmol) in dry CH2Cl2 (1.5 mL) was added

TMSOTf (5.6 µL, 0.03 mmol) at -25 °C, and the mixture was stirred for 12 hours at the same

temperature. After that, the reaction mixture was quenched with a saturated solution of

NaHCO3 and extracted with CH2Cl2, and the organic layer was washed with brine and dried

with Na2SO4. After removal of the solvent under reduced pressure, the residue was purified by

flash column chromatography on silica gel (petroleum ether/AcOEt = 15:1 as eluent) to give 5

as a colorless oil (17.4 mg, 56% yield), together with 12.3 mg of 3za recovered (82 % yield

based on recovered starting material). 1H NMR (400 MHz, CDCl3) δ 7.94 (d, J = 7.8 Hz, 2H), 7.56-7.51 (m, 2H), 7.43-7.36 (m, 4H), 7.30-7.23 (m, 1H), 7.15-7.01 (m, 4H), 6.12 (s, 1H), 5.55 (s, 2H), 4.41 (s, 2H), 3.87 (s, 3H), 3.72 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 166.2 , 139.7, 137.6, 137.3, 133.1, 130.8, 129.7, 129.6, 128.4, 127.7, 127.0, 122.7, 120.6, 119.9, 119.6, 119.5, 119.1, 112.0, 109.2, 108.7, 100.5, 56.2, 30.0, 29.7, 22.9; HRMS (ESI/ [M+Na]+) calcd for C27H24O2 N2Na+: 431.1730, found 431.1733.

6. Radical trapping experiments

Followed the General Procedure, to a mixture of indole 1d (0.144 g, 0.5 mmol),

perester 2a (0.29 mL, 1.5 mmol), and Co(acac)2 (13 mg, 10 mol%) in toluene (3 mL) was added TEMPO (0.234 g, 1.5 mmol) or BHT (0.330 g, 1.5 mmol). The reaction mixture was then stirred at 80 oC for 5 hours. No desired product 3da was detected.

7. References

[1] Xu, D.; Sun, W.-W.; Xie, T.; Liu, J.-K.; Liu, B.; Zhou, Y.; Wu, B. J. Org. Chem. 2016, 81,

11081–11094.

[2] Siddalingamurthy, E.; Mahadevan, K. M.; Masagalli, J. N.; Harishkumar, H. N. Tetrahedron

Lett. 2013, 54, 5591–5596.

S20

[3] Rodríguez, J. G.; Urrutia, A. Tetrahedron, 1999, 55, 11095–11108.

[4] Wei, W.; Zhang, C.; Xu, Y.; Wan. X. Chem. Commun., 2011, 47, 10827–10829.

8.

Awitdep18

Single cry

A single cryth pentane posited in t61986.

ystal data

ystal of 3aaas the anti-the Cambri

a of produ

a was obtainsolvent at ridge Crysta

S21

uct 3aa

ned by evaproom tempeallographic

porative diferature. This

Data Centr

ffusion in ds crystal strure and assig

dichloromethructure has bgned as CC

hane been CDC

S22

Table 1. Crystal data and structure refinement for 3aa.

Identification code 3aa

Empirical formula C20H15N3O2

Formula weight 329.35

Temperature/K 100.01(10)

Crystal system monoclinic

Space group P21/c

a/Å 8.8758(8)

b/Å 14.7297(12)

c/Å 11.9629(11)

α/° 90

β/° 101.831(9)

γ/° 90

Volume/Å3 1530.8(2)

Z 4

ρcalcg/cm3 1.429

μ/mm-1 0.095

F(000) 688.0

Crystal size/mm3 0.13 × 0.12 × 0.11

Radiation MoKα (λ = 0.71073)

2Θ range for data collection/° 4.444 to 58.936

Index ranges -9 ≤ h ≤ 12, -20 ≤ k ≤ 19, -16 ≤ l ≤ 11

Reflections collected 8002

Independent reflections 3637 [Rint = 0.0331, Rsigma = 0.0519]

Data/restraints/parameters 3637/0/226

Goodness-of-fit on F2 1.029

Final R indexes [I>=2σ (I)] R1 = 0.0482, wR2 = 0.1047

Final R indexes [all data] R1 = 0.0620, wR2 = 0.1144

Largest diff. peak/hole / e Å-3 0.24/-0.28

S23

Table 2. Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å2×103) for 3aa. Ueq is defined as 1/3 of of the trace of the orthogonalised UIJ tensor.

Atom x y z U(eq)

O(1) 3743.4(11) 5704.4(7) 4274.7(8) 17.0(2)

O(2) 3280.9(12) 5573.1(8) 2361.5(9) 21.6(3)

N(1) 1411.9(13) 4392.2(8) 5942.8(10) 14.5(3)

N(3) 623.5(14) 3603.3(9) 4244.9(10) 18.1(3)

N(2) -430.0(14) 3252.7(9) 5876.4(11) 18.8(3)

C(17) 489.5(15) 3714.1(10) 5324.4(12) 15.1(3)

C(11) 5021.9(16) 6713.8(10) 3279.0(12) 16.6(3)

C(8) 2488.5(16) 4947.2(10) 5532.2(12) 15.1(3)

C(1) 1545.0(16) 4588.1(10) 7114.2(12) 15.0(3)

C(7) 3266.4(16) 5451.9(10) 6401.7(12) 16.5(3)

C(10) 3928.0(16) 5939.4(10) 3227.6(12) 16.1(3)

C(9) 2690.3(16) 4960.3(10) 4322.7(12) 15.8(3)

C(2) 737.7(17) 4263.3(10) 7916.1(13) 17.6(3)

C(6) 2713.3(16) 5239.5(10) 7408.5(13) 16.8(3)

C(20) -280.5(17) 2967.0(11) 3663.5(13) 20.8(3)

C(16) 5488.2(16) 7223.7(10) 4266.2(13) 18.7(3)

C(12) 5599.4(17) 6923.7(11) 2309.5(13) 19.2(3)

C(4) 2358.9(18) 5211.2(11) 9338.0(13) 22.4(4)

C(18) -1301.6(17) 2616.4(11) 5263.5(13) 20.5(3)

C(5) 3135.2(18) 5545.4(11) 8535.3(13) 20.6(3)

C(19) -1283.6(17) 2445.2(11) 4137.5(14) 22.0(3)

C(3) 1165.5(18) 4585.4(11) 9022.6(13) 20.6(3)

C(13) 6630.2(17) 7635.7(11) 2339.7(13) 21.6(3)

C(14) 7077.0(17) 8146.6(11) 3319.2(14) 22.1(4)

C(15) 6511.3(17) 7936.1(11) 4286.0(14) 21.5(3)

S24

Table 3. Anisotropic Displacement Parameters (Å2×103) for 3aa. The Anisotropic displacement factor exponent takes the form: -2π2[h2a*2U11+2hka*b*U12+…].

Atom U11 U22 U33 U23 U13 U12

O(1) 17.4(5) 17.6(5) 16.5(5) 0.8(4) 4.9(4) -3.7(4)

O(2) 22.7(6) 25.2(6) 16.3(6) -1.2(5) 2.6(4) -4.2(5)

N(1) 14.4(6) 15.4(6) 14.2(6) 0.0(5) 3.9(5) -0.1(5)

N(3) 17.6(6) 17.9(6) 18.5(7) -2.0(5) 2.7(5) -0.1(5)

N(2) 18.3(6) 16.6(6) 22.1(7) 0.7(5) 5.3(5) -1.3(5)

C(17) 13.4(7) 12.4(7) 19.0(7) 1.1(6) 2.3(5) 2.3(6)

C(11) 13.9(7) 16.6(7) 19.0(8) 3.3(6) 2.5(6) 2.2(6)

C(8) 12.2(7) 14.5(7) 18.5(7) 1.7(6) 3.0(5) 2.7(6)

C(1) 15.2(7) 14.5(7) 14.9(7) 0.1(6) 1.9(5) 3.6(6)

C(7) 15.6(7) 15.4(7) 18.6(8) 0.9(6) 3.8(6) 1.0(6)

C(10) 15.0(7) 16.8(7) 16.6(7) 2.1(6) 3.8(5) 3.6(6)

C(9) 15.3(7) 14.1(7) 18.5(8) -0.4(6) 4.8(6) -2.3(6)

C(2) 18.1(7) 15.3(7) 19.7(8) 1.5(6) 5.0(6) 2.1(6)

C(6) 16.5(7) 14.7(7) 18.8(8) 0.0(6) 2.8(6) 3.4(6)

C(20) 21.2(8) 20.9(8) 19.9(8) -4.6(6) 3.4(6) 0.9(6)

C(16) 17.0(7) 18.8(8) 20.4(8) 2.6(6) 4.1(6) 1.4(6)

C(12) 18.9(7) 21.3(8) 17.1(7) 1.4(6) 3.1(6) 1.4(6)

C(4) 29.4(9) 20.3(8) 16.5(8) -2.6(6) 2.7(6) 3.6(7)

C(18) 18.3(7) 16.3(7) 27.9(9) -0.2(6) 6.7(6) -3.2(6)

C(5) 22.2(8) 19.3(8) 19.2(8) -3.5(6) 1.9(6) -0.9(6)

C(19) 18.0(7) 18.6(8) 28.5(9) -6.0(7) 2.8(6) -2.0(6)

C(3) 24.3(8) 20.4(8) 18.3(8) 2.6(6) 7.6(6) 3.8(6)

C(13) 20.7(8) 24.0(8) 21.2(8) 6.7(7) 7.0(6) 1.2(7)

C(14) 17.2(7) 17.8(8) 30.4(9) 5.3(7) 2.8(6) -0.3(6)

C(15) 22.4(8) 19.3(8) 21.8(8) -0.2(6) 2.6(6) -0.9(7)

S25

Table 4 Bond Lengths for 3aa.

Atom Atom Length/Å Atom Atom Length/Å

O(1) C(10) 1.3416(17) C(8) C(9) 1.494(2)

O(1) C(9) 1.4492(17) C(1) C(2) 1.394(2)

O(2) C(10) 1.2044(17) C(1) C(6) 1.404(2)

N(1) C(17) 1.4024(18) C(7) C(6) 1.425(2)

N(1) C(8) 1.4195(19) C(2) C(3) 1.384(2)

N(1) C(1) 1.4118(18) C(6) C(5) 1.398(2)

N(3) C(17) 1.3309(19) C(20) C(19) 1.383(2)

N(3) C(20) 1.3331(19) C(16) C(15) 1.385(2)

N(2) C(17) 1.3361(19) C(12) C(13) 1.387(2)

N(2) C(18) 1.3349(19) C(4) C(5) 1.382(2)

C(11) C(10) 1.491(2) C(4) C(3) 1.396(2)

C(11) C(16) 1.389(2) C(18) C(19) 1.374(2)

C(11) C(12) 1.395(2) C(13) C(14) 1.381(2)

C(8) C(7) 1.348(2) C(14) C(15) 1.387(2)

Table 5. Bond Angles for 3aa.

Atom Atom Atom Angle/˚ Atom Atom Atom Angle/˚

C(10) O(1) C(9) 115.81(11) O(1) C(10) C(11) 111.23(12)

C(17) N(1) C(8) 126.10(12) O(2) C(10) O(1) 124.03(14)

C(17) N(1) C(1) 126.17(12) O(2) C(10) C(11) 124.74(14)

C(1) N(1) C(8) 107.49(11) O(1) C(9) C(8) 104.75(11)

C(17) N(3) C(20) 115.37(13) C(3) C(2) C(1) 117.48(14)

C(18) N(2) C(17) 115.44(13) C(1) C(6) C(7) 107.62(13)

N(3) C(17) N(1) 116.13(13) C(5) C(6) C(1) 120.03(14)

N(3) C(17) N(2) 127.04(13) C(5) C(6) C(7) 132.34(15)

N(2) C(17) N(1) 116.83(13) N(3) C(20) C(19) 123.10(15)

C(16) C(11) C(10) 121.78(14) C(15) C(16) C(11) 120.29(15)

C(16) C(11) C(12) 119.38(14) C(13) C(12) C(11) 119.90(15)

C(12) C(11) C(10) 118.84(13) C(5) C(4) C(3) 120.40(14)

S26

N(1) C(8) C(9) 124.43(12) N(2) C(18) C(19) 123.07(14)

C(7) C(8) N(1) 108.98(13) C(4) C(5) C(6) 118.82(15)

C(7) C(8) C(9) 126.59(13) C(18) C(19) C(20) 115.97(14)

C(2) C(1) N(1) 131.49(14) C(2) C(3) C(4) 121.93(15)

C(2) C(1) C(6) 121.29(14) C(14) C(13) C(12) 120.49(15)

C(6) C(1) N(1) 107.21(13) C(13) C(14) C(15) 119.72(15)

C(8) C(7) C(6) 108.69(13) C(16) C(15) C(14) 120.22(15)

Table 6. Hydrogen Atom Coordinates (Å×104) and Isotropic Displacement

Parameters (Å2×103) for 3aa.

Atom x y z U(eq)

H(7) 4036.27 5869.37 6352.9 20

H(9A) 3120.12 4391.1 4125.87 19

H(9B) 1713.66 5063.23 3802.07 19

H(2) -58.08 3846.04 7714.93 21

H(20) -234.23 2869.39 2903.24 25

H(16) 5111.62 7086.09 4916.59 22

H(12) 5293.69 6586.88 1644.08 23

H(4) 2632.95 5404.2 10092.59 27

H(18) -1951.41 2273.04 5615.17 25

H(5) 3924.23 5966.4 8741.38 25

H(19) -1908.46 2004.8 3719.23 26

H(3) 642.96 4379.04 9572.2 25

H(13) 7023.1 7769.75 1695.44 26

H(14) 7754.4 8629.79 3330.71 27

H(15) 6820.19 8274.51 4949.76 26

9.

Acryand

Single cry

A single cryystal structud assigned a

ystal data

ystal of 3gaure has beenas CCDC 1

a of produ

a was obtainn deposited861984.

S27

uct 3ga

ned by recryd in the Cam

ystallizationmbridge Cry

n in methanystallograph

nol at 0 oC. hic Data Ce

This entre

S28

Table 7. Crystal data and structure refinement for 3ga.Identification code 3ga

Empirical formula C21H17N3O2

Formula weight 343.38

Temperature/K 100.00(10)

Crystal system monoclinic

Space group P21/c

a/Å 8.7751(5)

b/Å 13.7237(7)

c/Å 14.5990(10)

α/° 90

β/° 101.524(6)

γ/° 90

Volume/Å3 1722.67(18)

Z 4

ρcalcg/cm3 1.324

μ/mm-1 0.087

F(000) 720.0

Crystal size/mm3 0.13 × 0.12 × 0.11

Radiation MoKα (λ = 0.71073)

2Θ range for data collection/° 4.112 to 50

Index ranges -8 ≤ h ≤ 10, -16 ≤ k ≤ 16, -17 ≤ l ≤ 14

Reflections collected 9225

Independent reflections 2973 [Rint = 0.0455, Rsigma = 0.0526]

Data/restraints/parameters 2973/0/236

Goodness-of-fit on F2 1.056

Final R indexes [I>=2σ (I)] R1 = 0.0464, wR2 = 0.0981

Final R indexes [all data] R1 = 0.0606, wR2 = 0.1070

Largest diff. peak/hole / e Å-3 0.20/-0.23

S29

Table 8. Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å2×103) for 5-570. Ueq is defined as 1/3 of of the trace of the orthogonalised UIJ tensor. Atom x y z U(eq)

O1 5583.3(14) 3186.3(8) 4490.5(9) 21.4(3)

O2 3631.9(14) 3715.8(9) 3358.7(10) 29.4(4)

N1 7659.9(16) 1558.9(10) 4891.3(11) 17.1(4)

N3 7333.0(16) 1997.1(10) 3318.8(11) 20.3(4)

N2 9726.2(17) 2313.8(11) 4391.5(11) 22.3(4)

C17 8267.1(19) 1980.4(12) 4160.2(13) 17.6(4)

C8 6088.6(19) 1567.2(12) 4992.6(13) 18.1(4)

C6 7437(2) 616.0(12) 6133.1(13) 18.4(4)

C7 5920(2) 1006.4(12) 5733.8(13) 19.0(4)

C10 4858(2) 3861.9(13) 3892.1(13) 20.1(4)

C20 7950(2) 2389.2(13) 2637.2(14) 23.2(5)

C5 8501(2) 983.9(12) 5615.6(12) 17.0(4)

C4 10084(2) 759.3(12) 5846.3(13) 19.7(4)

C11 5753(2) 4791.2(13) 3955.4(13) 20.3(4)

C1 7967(2) 13.4(13) 6907.1(14) 22.7(5)

C16 5087(2) 5593.8(13) 3441.1(13) 21.2(4)

C9 4916(2) 2209.5(12) 4401.9(14) 21.1(4)

C19 9462(2) 2731.9(13) 2780.3(14) 24.5(5)

C18 10304(2) 2672.6(13) 3678.8(14) 24.2(5)

C3 10579(2) 169.5(13) 6618.8(14) 22.7(5)

C2 9537(2) -196.3(13) 7144.7(14) 24.3(5)

C21 4476(2) 823.1(13) 6107.5(14) 24.5(5)

C12 7263(2) 4861.9(13) 4484.2(14) 24.8(5)

C15 5913(2) 6454.0(13) 3453.2(14) 23.9(5)

C14 7413(2) 6521.2(13) 3978.6(14) 26.0(5)

C13 8082(2) 5727.5(13) 4489.3(15) 28.1(5)

Table 9. Anisotropic Displacement Parameters (Å2×103) for 3ga. The Anisotropic displacement factor exponent takes the form: -2π2[h2a*2U11+2hka*b*U12+…]. Atom U11 U22 U33 U23 U13 U12

O1 21.2(7) 18.1(7) 22.9(8) 0.0(6) -0.4(6) 0.8(5)

O2 19.1(7) 32.6(8) 33.3(9) 9.4(7) -2.8(6) -4.7(6)

N1 14.3(8) 19.2(8) 17.8(9) 1.3(7) 3.1(6) -0.9(6)

N3 20.0(8) 20.6(8) 19.9(9) 2.7(7) 3.0(7) -0.2(6)

N2 19.4(9) 22.5(8) 24.9(10) 1.3(7) 4.3(7) -4.3(6)

S30

C17 17.0(10) 15.2(9) 20.8(11) -1.1(8) 4.1(8) 0.7(7)

C8 14.3(9) 18.5(9) 21.4(11) -4.6(8) 3.7(8) -3.0(7)

C6 20.7(10) 14.6(9) 19.8(11) -3.7(8) 3.9(8) -1.6(7)

C7 20.3(10) 16.5(9) 21.0(11) -5.3(8) 5.9(8) -2.7(7)

C10 16.1(10) 26.9(10) 18.4(11) 0.0(8) 5.8(8) 2.6(7)

C20 24.6(11) 22.3(10) 21.1(11) 4.6(9) 0.9(8) 3.9(8)

C5 20.6(10) 15.0(9) 14.7(10) -2.6(8) 2.1(7) -1.1(7)

C4 19.5(10) 19.6(10) 20.9(11) -4.3(8) 6.2(8) -0.3(7)

C11 20.3(10) 23.4(10) 18.9(11) -2.5(8) 8.3(8) 2.1(7)

C1 28.1(11) 17.7(10) 24.3(11) -0.2(8) 9.9(8) -1.0(8)

C16 18.6(10) 26.6(10) 18.4(11) -2.5(8) 3.5(8) 2.6(7)

C9 17.8(10) 20.7(10) 25.1(11) -1.8(8) 4.5(8) -2.3(7)

C19 24.9(11) 22.9(10) 27.0(12) 6.9(9) 8.2(9) 1.3(8)

C18 17.6(10) 23.1(10) 32.2(12) 3.7(9) 6.1(9) -4.3(7)

C3 21.2(10) 20.3(10) 25.8(12) -2.5(9) 2.9(8) 5.4(7)

C2 31.2(11) 18.7(10) 22.7(11) 3.8(8) 4.4(9) 5.2(8)

C21 24.4(10) 24.8(11) 26.2(12) -0.7(9) 9.3(8) -1.2(8)

C12 21.8(10) 22.9(10) 28.4(12) 0.4(9) 1.8(8) 2.8(8)

C15 26.6(11) 21.5(10) 23.8(11) -1.8(9) 5.8(8) 5.3(8)

C14 26.7(11) 21.3(10) 31.3(12) -6.4(9) 9.2(9) -1.6(8)

C13 19.9(10) 27.5(11) 34.8(13) -5.1(9) 0.4(9) 0.0(8)

Table 10. Bond Lengths for 3ga. Atom Atom Length/Å Atom Atom Length/Å

O1 C10 1.344(2) C7 C21 1.497(3)

O1 C9 1.458(2) C10 C11 1.491(3)

O2 C10 1.212(2) C20 C19 1.383(3)

N1 C17 1.409(2) C5 C4 1.397(2)

N1 C8 1.416(2) C4 C3 1.386(3)

N1 C5 1.405(2) C11 C16 1.394(2)

N3 C17 1.334(2) C11 C12 1.397(2)

N3 C20 1.337(2) C1 C2 1.381(3)

N2 C17 1.338(2) C16 C15 1.383(3)

N2 C18 1.339(2) C19 C18 1.373(3)

C8 C7 1.360(3) C3 C2 1.399(3)

C8 C9 1.491(2) C12 C13 1.388(3)

C6 C7 1.445(2) C15 C14 1.388(3)

C6 C5 1.407(3) C14 C13 1.383(3)

C6 C1 1.402(3)

S31

Table 11. Bond Angles for 3ga. Atom Atom Atom Angle/˚ Atom Atom Atom Angle/˚

C10 O1 C9 116.57(13) O2 C10 C11 124.77(16)

C17 N1 C8 126.83(14) N3 C20 C19 122.90(17)

C5 N1 C17 125.40(14) N1 C5 C6 107.47(15)

C5 N1 C8 107.59(15) C4 C5 N1 130.78(17)

C17 N3 C20 115.24(15) C4 C5 C6 121.74(16)

C17 N2 C18 114.91(16) C3 C4 C5 117.38(18)

N3 C17 N1 116.67(15) C16 C11 C10 118.92(15)

N3 C17 N2 127.42(18) C16 C11 C12 119.48(17)

N2 C17 N1 115.91(15) C12 C11 C10 121.55(16)

N1 C8 C9 121.19(16) C2 C1 C6 118.60(19)

C7 C8 N1 109.97(15) C15 C16 C11 120.35(16)

C7 C8 C9 128.51(17) O1 C9 C8 105.89(13)

C5 C6 C7 107.88(16) C18 C19 C20 116.15(19)

C1 C6 C7 132.38(18) N2 C18 C19 123.32(17)

C1 C6 C5 119.69(16) C4 C3 C2 121.55(17)

C8 C7 C6 107.04(16) C1 C2 C3 121.03(18)

C8 C7 C21 128.28(16) C13 C12 C11 119.69(17)

C6 C7 C21 124.67(17) C16 C15 C14 120.02(17)

O1 C10 C11 112.02(14) C13 C14 C15 119.94(18)

O2 C10 O1 123.21(16) C14 C13 C12 120.53(17)

Table 12. Hydrogen Atom Coordinates (Å×104) and Isotropic Displacement Parameters (Å2×103) for 3ga. Atom x y z U(eq)

H20 7336.43 2433.23 2040.69 28

H4 10778.75 996.34 5495.21 24

H1 7277.01 -239.65 7253.05 27

H16 4082.28 5550.69 3088.07 25

H9A 4724.03 1997.24 3755.23 25

H9B 3942.38 2197.27 4619.95 25

H19 9883.27 2987.85 2295.88 29

H18 11326.46 2892.82 3798.18 29

H3 11628.17 12.96 6791.92 27

H2 9905.98 -586.67 7662.11 29

H21A 4613.8 1070.18 6733.89 37

H21B 4277.57 135.33 6109.06 37

H21C 3612.05 1146.44 5719.25 37

S32

H12 7717.15 4331.24 4831.07 30

H15 5462.09 6987.42 3109.38 29

H14 7968.38 7099.5 3986.88 31

H13 9088.49 5774.27 4839.15 34

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

2.14

1.001.081.671.122.040.990.971.91

1.031.81

0.015

5.971

6.859

7.049

7.061

7.073

7.231

7.249

7.260

7.263

7.267

7.268

7.316

7.319

7.322

7.333

7.337

7.340

7.343

7.358

7.385

7.406

7.426

7.521

7.524

7.540

7.542

7.558

7.561

7.606

7.626

7.974

7.995

8.561

8.583

8.715

8.727

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

61.953

76.681

76.999

77.318

108.660

115.083

116.791

120.538

123.833

128.302

132.928

135.314

137.076

158.011

158.085

166.146

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.15

2.12

1.00

1.081.182.071.071.091.96

1.001.93

0.013

2.269

5.936

6.836

7.210

7.228

7.247

7.260

7.298

7.319

7.337

7.378

7.397

7.417

7.514

7.534

7.554

7.604

7.623

7.957

7.978

8.451

8.472

8.540

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

14.970

61.733

76.684

77.000

77.318

108.081

114.615

120.509

121.927

123.649

126.176

128.658

132.883

135.125

137.045

156.256

158.001

166.132

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

2.05

0.971.741.162.081.101.022.01

1.001.85

0.015

5.911

6.855

7.234

7.253

7.262

7.271

7.316

7.337

7.355

7.391

7.411

7.430

7.531

7.549

7.568

7.609

7.628

7.964

7.985

8.434

8.455

8.586

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

61.606

76.683

77.000

77.318

108.987

114.558

120.699

122.376

124.021

128.372

133.046

135.100

137.046

145.639

145.857

153.431

154.162

156.021

166.117

110120130140150160f1 (ppm)

108.987

114.558

120.699

122.376

124.021

128.372

128.709

129.551

133.046

135.100

137.046

145.639

145.857

153.431

154.162

156.021

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

1.99

0.98

2.021.152.112.09

1.91

1.001.97

0.007

5.907

6.860

7.235

7.260

7.273

7.315

7.336

7.354

7.404

7.423

7.442

7.538

7.557

7.575

7.592

7.611

7.989

8.009

8.502

8.523

8.731

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

61.770

76.682

77.000

77.317

109.524

114.173

115.268

120.679

122.603

124.117

128.380

133.048

135.249

136.975

156.291

158.451

166.117

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.30

2.12

1.001.031.123.081.24

1.99

1.071.91

0.009

2.465

5.952

6.775

7.024

7.036

7.048

7.137

7.158

7.260

7.381

7.382

7.385

7.388

7.390

7.392

7.400

7.402

7.420

7.423

7.516

7.536

7.557

7.973

7.993

8.449

8.471

8.694

8.706

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

21.293

62.079

76.683

77.000

77.318

108.536

114.934

116.528

120.355

125.271

128.293

129.552

131.608

135.319

135.382

157.943

158.145

166.179

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

2.06

1.001.011.522.011.93

1.93

1.001.92

0.005

5.947

6.776

7.087

7.099

7.110

7.251

7.260

7.272

7.398

7.417

7.436

7.532

7.535

7.554

7.559

7.569

7.572

7.983

8.003

8.511

8.533

8.721

8.733

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

61.898

76.682

77.000

77.318

107.621

116.444

117.058

119.916

123.878

127.724

129.583

133.054

135.407

136.911

157.869

158.085

166.088

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.03

2.09

1.004.391.011.001.93

1.001.95

0.019

2.471

5.987

7.006

7.014

7.025

7.260

7.278

7.299

7.321

7.341

7.365

7.383

7.457

7.475

7.493

7.612

7.632

7.809

7.828

8.435

8.455

8.681

8.692

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

8.928

58.390

76.683

77.000

77.319

114.426

116.665

118.168

119.014

121.777

124.460

128.154

132.708

136.525

157.985

158.073

166.335

127.5128.5129.5130.5131.5f1 (ppm)

128.154

129.395

129.721

129.869

130.173

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.28

2.17

2.02

0.983.131.131.071.90

1.02

1.85

0.004

1.309

1.328

1.347

2.899

2.918

2.937

2.956

5.908

7.260

7.278

7.296

7.333

7.337

7.351

7.370

7.375

7.378

7.480

7.483

7.498

7.501

7.517

7.520

7.640

7.661

7.840

7.861

8.400

8.420

8.696

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

15.694

17.543

58.035

76.682

77.001

77.319

114.121

114.795

119.189

122.150

124.652

128.272

132.869

136.586

156.285

158.435

166.341

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

6.25

1.13

2.00

1.583.131.093.10

1.00

1.91

0.023

1.531

1.549

3.441

3.459

3.476

3.494

3.512

5.923

7.234

7.253

7.260

7.271

7.320

7.341

7.361

7.380

7.489

7.507

7.526

7.826

7.853

7.873

8.342

8.363

8.720

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

22.765

26.181

57.745

76.682

77.001

77.319

114.386

114.461

120.814

121.715

124.209

127.648

128.951

132.853

136.890

156.154

158.500

166.232

127.5128.5129.5130.5131.5f1 (ppm)

127.648

128.242

128.408

128.951

129.408

130.061

113.0114.0115.0116.0f1 (ppm)

114.386

114.461

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.32

2.39

2.11

2.06

1.054.991.121.071.93

1.001.86

0.009

0.998

1.017

1.035

1.706

1.725

1.743

1.762

1.780

1.799

2.871

2.890

2.908

5.953

6.999

7.011

7.023

7.240

7.260

7.278

7.294

7.313

7.331

7.349

7.367

7.452

7.471

7.489

7.637

7.656

7.789

7.809

8.420

8.441

8.676

8.688

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

14.050

24.007

26.169

58.326

76.682

77.000

77.319

114.453

116.728

119.237

121.719

124.330

128.169

132.714

136.678

158.007

158.104

166.331

157.4157.8158.2158.6f1 (ppm)

158.007

158.104

128.0128.5129.0129.5130.0130.5131.0131.5f1 (ppm)

128.169

129.160

129.400

129.880

130.194

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

6.29

1.25

2.00

2.00

1.227.141.171.171.90

1.031.87

0.004

0.999

1.015

1.996

2.013

2.030

2.047

2.064

2.081

2.098

2.762

2.780

5.935

6.994

7.006

7.018

7.232

7.250

7.260

7.285

7.304

7.323

7.343

7.361

7.446

7.465

7.483

7.619

7.639

7.766

7.784

8.408

8.429

8.670

8.682

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

22.729

29.698

33.426

58.398

76.682

77.000

77.318

114.332

116.747

119.486

121.681

124.291

128.158

132.713

136.611

157.999

158.068

166.293

157.6157.8158.0158.2158.4f1 (ppm)

157.999

158.068

121122123124125126127128129130131f1 (ppm)

121.681

122.007

124.291

128.158

129.363

129.442

130.128

130.238

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

2.08

2.06

4.115.172.091.90

1.00

1.87

0.010

4.303

5.952

7.139

7.157

7.175

7.196

7.216

7.235

7.236

7.260

7.286

7.305

7.324

7.342

7.362

7.479

7.482

7.500

7.501

7.519

7.538

7.799

7.820

8.394

8.415

8.719

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

30.132

58.062

76.684

77.000

77.318

114.396

114.679

119.687

121.854

122.363

124.779

126.111

128.242

128.269

128.449

129.229

129.455

130.016

130.807

132.876

136.617

139.919

156.238

158.507

166.231

128.0128.5129.0129.5130.0130.5131.0f1 (ppm)

128.242

128.269

128.449

129.229

129.455

130.016

130.807

114.2114.4114.6114.8115.0f1 (ppm)

114.396

114.679

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.01

1.96

2.001.273.183.071.052.00

1.001.91

-0.002

3.875

5.806

7.036

7.057

7.264

7.284

7.303

7.342

7.346

7.361

7.364

7.374

7.377

7.381

7.384

7.391

7.395

7.398

7.402

7.413

7.416

7.420

7.494

7.498

7.501

7.506

7.510

7.516

7.522

7.527

7.531

7.653

7.672

7.850

7.870

8.439

8.460

8.692

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

55.339

59.287

76.682

77.000

77.317

114.238

114.563

114.686

120.181

122.699

125.007

125.149

125.314

128.303

128.842

129.449

129.727

130.140

131.216

132.902

136.409

156.236

158.565

159.161

166.147

125126127128129130131f1 (ppm)

125.007

125.149

125.314

128.303

128.842

129.449

129.727

130.140

113.5114.0114.5115.0115.5f1 (ppm)

114.238

114.563

114.686

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.01

2.03

3.043.013.120.981.94

1.00

1.93

0.002

3.876

5.844

7.040

7.053

7.062

7.260

7.307

7.312

7.318

7.327

7.335

7.341

7.346

7.468

7.476

7.487

7.497

7.613

7.619

7.793

7.812

8.409

8.432

8.681

8.693

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

55.352

59.270

76.683

77.001

77.319

114.355

115.842

117.327

119.477

123.835

124.747

124.832

127.992

128.221

129.418

129.934

130.105

131.185

132.808

134.892

157.833

158.185

159.268

166.059

156157158159160161f1 (ppm)

157.833

158.185

159.268

127.5128.0128.5129.0129.5130.0130.5131.0f1 (ppm)

127.992

128.221

129.418

129.934

130.105

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

2.12

2.151.183.273.161.051.95

1.00

1.92

-0.002

5.115

5.797

7.184

7.206

7.228

7.260

7.278

7.297

7.316

7.349

7.369

7.389

7.410

7.413

7.428

7.431

7.434

7.502

7.505

7.523

7.544

7.555

7.557

7.563

7.566

7.576

7.579

7.613

7.633

7.840

7.861

8.438

8.459

8.710

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

59.015

76.682

76.999

77.318

114.704

114.786

115.645

115.859

119.897

122.832

124.434

125.138

128.316

128.525

128.839

128.871

129.413

129.967

130.088

131.644

131.724

132.972

136.322

156.113

158.598

161.119

163.577

166.046

127.0127.5128.0128.5129.0129.5130.0130.5131.0f1 (ppm)

128.316

128.525

128.839

128.871

129.413

129.967

130.088

113.5114.0114.5115.0115.5116.0116.5f1 (ppm)

114.704

114.786

115.645

115.859

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

2.09

1.283.475.140.971.93

1.00

1.87

-0.014

5.793

7.260

7.279

7.298

7.317

7.347

7.367

7.386

7.392

7.411

7.414

7.432

7.471

7.492

7.501

7.505

7.522

7.541

7.613

7.633

7.827

7.847

8.426

8.447

8.714

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

58.959

76.682

77.000

77.318

114.703

114.897

119.848

122.901

124.185

125.195

128.309

128.327

128.980

129.418

129.926

130.202

131.341

131.434

132.999

133.595

136.366

156.083

158.639

166.017

128.5129.0129.5130.0130.5131.0131.5f1 (ppm)

128.309

128.327

128.980

129.418

129.926

130.202

131.341

131.434

114.3114.5114.7114.9115.1115.3f1 (ppm)

114.703

114.897

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

2.20

1.213.201.941.192.901.90

1.00

1.85

0.001

5.791

7.260

7.277

7.297

7.316

7.347

7.366

7.383

7.386

7.390

7.412

7.430

7.458

7.479

7.500

7.504

7.520

7.523

7.538

7.541

7.611

7.624

7.628

7.632

7.645

7.649

7.823

7.843

8.422

8.443

8.715

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

58.955

76.683

77.001

77.318

114.707

114.917

116.334

119.833

121.767

122.917

124.182

125.206

128.237

128.329

129.419

129.924

130.189

131.666

131.932

133.001

136.385

156.084

158.646

166.007

128129130131132f1 (ppm)

128.237

128.329

129.419

129.924

130.189

131.666

131.932

113.5114.0114.5115.0115.5116.0116.5f1 (ppm)

114.707

114.917

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.11

2.18

3.10

2.02

2.18

1.001.981.011.071.82

1.02

1.96

0.009

0.999

1.017

1.035

1.689

1.707

1.726

1.744

1.763

1.781

2.491

2.828

2.847

2.865

5.887

7.161

7.182

7.260

7.332

7.350

7.370

7.408

7.482

7.485

7.501

7.517

7.519

7.839

7.860

8.304

8.326

8.660

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

14.063

21.390

23.882

26.165

58.234

76.682

77.001

77.318

113.706

114.652

119.118

123.675

126.034

128.244

129.417

129.498

129.835

130.167

131.572

132.811

134.800

156.279

158.293

166.348

129.5130.0130.5f1 (ppm)

129.417

129.498

129.835

130.167

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.19

2.23

2.06

3.21

2.11

1.001.001.991.02

1.93

1.08

1.83

0.007

1.000

1.018

1.036

1.688

1.706

1.725

1.743

1.761

1.779

2.822

2.841

2.859

3.905

5.885

6.972

6.995

7.056

7.260

7.334

7.353

7.372

7.483

7.501

7.519

7.851

7.870

8.362

8.384

8.645

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

14.052

23.761

26.171

55.795

58.255

76.683

77.001

77.318

101.737

113.410

113.628

116.035

123.713

128.264

129.437

130.143

130.163

130.491

131.394

132.838

155.561

156.194

158.291

166.361

129.0129.5130.0130.5131.0131.5132.0f1 (ppm)

129.437

130.143

130.163

130.491

131.394

113.0113.2113.4113.6113.8114.0114.2f1 (ppm)

113.410

113.628

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.21

2.24

2.11

2.00

1.081.572.061.041.89

0.99

1.82

-0.014

0.991

1.010

1.028

1.672

1.691

1.709

1.727

1.746

1.764

2.809

2.827

2.846

5.881

7.042

7.045

7.049

7.052

7.065

7.068

7.072

7.075

7.088

7.091

7.095

7.098

7.248

7.251

7.257

7.259

7.261

7.270

7.274

7.277

7.280

7.331

7.352

7.373

7.484

7.487

7.502

7.506

7.521

7.524

7.833

7.853

8.364

8.366

8.375

8.378

8.387

8.389

8.398

8.401

8.680

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

14.006

23.775

26.134

58.049

76.682

77.001

77.319

104.462

104.695

112.277

112.526

114.211

115.987

116.075

123.465

123.506

128.286

129.416

129.995

130.128

130.222

131.428

132.840

132.921

156.041

157.753

158.417

160.129

166.255

130.0130.5131.0131.5132.0132.5133.0f1 (ppm)

129.995

130.128

130.222

131.428

132.840

132.921

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.31

2.35

2.18

2.09

1.082.081.071.001.96

1.04

1.90

-0.000

0.991

1.009

1.028

1.672

1.690

1.709

1.727

1.746

1.764

2.808

2.827

2.845

5.873

7.260

7.270

7.273

7.276

7.278

7.292

7.295

7.298

7.301

7.334

7.353

7.371

7.481

7.485

7.488

7.491

7.500

7.503

7.507

7.511

7.522

7.525

7.585

7.830

7.851

8.331

8.353

8.679

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

13.997

23.835

26.047

57.947

76.681

77.000

77.319

114.415

116.051

118.816

123.083

124.641

127.702

128.279

129.399

129.968

130.505

131.213

132.920

134.833

155.970

158.440

166.206

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.14

2.17

2.08

2.11

1.931.011.051.001.93

0.99

1.96

0.009

0.994

1.012

1.031

1.674

1.692

1.711

1.729

1.748

1.766

2.807

2.825

2.844

5.875

7.260

7.333

7.352

7.371

7.405

7.427

7.486

7.504

7.523

7.740

7.829

7.848

8.279

8.301

8.681

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

14.015

23.862

26.054

57.919

76.682

77.000

77.319

114.484

115.371

116.431

121.916

122.994

127.300

128.294

129.412

129.973

131.062

131.094

132.938

135.199

155.981

158.475

166.209

129.0129.5130.0130.5131.0131.5132.0f1 (ppm)

129.412

129.973

131.062

131.094

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.45

2.26

2.11

2.00

2.001.021.071.911.00

0.97

1.85

-0.001

1.007

1.019

1.031

1.701

1.713

1.726

1.738

1.750

1.762

2.866

2.879

2.891

5.882

7.260

7.338

7.351

7.364

7.497

7.509

7.522

7.561

7.563

7.575

7.578

7.799

7.812

7.966

7.969

8.412

8.427

8.743

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

13.995

23.966

25.970

57.591

76.682

76.999

77.317

105.251

115.438

115.525

120.012

123.204

124.461

127.365

128.342

129.220

129.389

129.729

132.320

133.088

138.182

155.684

158.758

166.079

128.8129.0129.2129.4129.6129.8130.0130.2130.4f1 (ppm)

129.220

129.389

129.729

115.1115.2115.3115.4115.5115.6115.7115.8115.9f1 (ppm)

115.438

115.525

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

2.361.211.14

1.151.19

0.981.002.062.331.161.071.012.00

1.811.02

0.008

1.983

2.007

2.015

2.060

2.085

2.115

2.168

2.176

2.184

2.211

2.231

2.240

2.301

2.309

2.316

2.323

2.332

2.345

2.356

2.718

2.733

2.743

2.759

2.774

2.784

2.799

2.963

2.974

2.985

3.005

3.016

3.027

6.836

6.848

6.860

7.024

7.034

7.044

7.260

7.276

7.295

7.314

7.333

7.352

7.372

7.391

7.443

7.461

7.479

7.585

7.605

7.857

7.877

8.530

8.541

8.597

8.618

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

18.463

21.325

30.229

67.124

76.683

77.000

77.319

115.520

116.152

118.661

120.637

121.887

124.500

128.121

128.742

129.377

130.908

132.194

132.490

136.576

157.783

158.053

166.031

157.4157.6157.8158.0158.2158.4f1 (ppm)

157.783

158.053

128129130131132f1 (ppm)

128.121

128.742

129.377

130.908

132.194

132.490

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.5f1 (ppm)

3.07

1.001.012.601.121.981.030.991.921.01

1.75

0.010

1.851

1.867

6.915

6.994

7.010

7.026

7.042

7.228

7.247

7.260

7.298

7.318

7.337

7.352

7.371

7.390

7.499

7.517

7.535

7.614

7.633

7.891

7.910

8.298

8.318

8.666

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

19.759

67.308

76.682

77.000

77.318

107.097

114.387

114.657

120.739

122.391

124.044

128.240

128.628

129.348

130.233

132.892

136.938

140.396

156.193

158.474

165.732

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.27

2.25

1.071.192.861.132.161.061.012.06

0.003

3.820

5.534

6.672

7.109

7.128

7.148

7.247

7.260

7.264

7.268

7.285

7.339

7.360

7.411

7.432

7.452

7.547

7.565

7.584

7.620

7.640

8.037

8.058

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

29.928

58.802

76.682

77.001

77.319

104.009

109.274

119.737

121.041

122.370

127.071

128.421

129.667

129.774

133.194

133.603

138.041

166.145

129.5130.0130.5131.0131.5132.0132.5133.0133.5f1 (ppm)

129.667

129.774

133.194

133.603

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.05

2.20

0.98

1.361.092.091.031.02

1.971.00

0.014

4.031

5.715

6.760

7.247

7.248

7.260

7.271

7.273

7.330

7.332

7.342

7.344

7.346

7.356

7.358

7.448

7.460

7.474

7.533

7.534

7.536

7.546

7.547

7.549

7.567

7.570

7.572

7.580

7.582

7.584

7.592

7.595

7.597

8.089

8.092

8.104

8.106

8.166

8.180

0102030405060708090100110120130140150160170180190200210f1 (ppm)

53.861

60.991

76.789

77.001

77.212

110.805

115.641

120.764

123.308

124.860

128.431

128.734

129.692

129.944

133.128

134.812

136.758

151.962

166.056

128.0128.5129.0129.5130.0130.5f1 (ppm)

128.431

128.734

129.692

129.944

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.11

2.06

1.072.001.561.111.00

1.90

1.011.82

0.030

3.857

5.875

6.846

6.899

6.919

7.241

7.260

7.270

7.274

7.279

7.317

7.337

7.356

7.592

7.612

7.959

7.979

8.502

8.522

8.713

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

55.379

61.506

76.683

77.000

77.318

109.230

113.597

115.224

120.597

122.369

123.990

128.948

131.590

135.517

136.904

156.234

158.367

163.393

165.806

122.3122.4122.5122.6122.7f1 (ppm)

122.369

122.529

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.10

2.19

0.94

2.042.801.001.83

0.981.87

0.006

2.381

5.893

6.854

7.235

7.254

7.260

7.273

7.284

7.303

7.315

7.321

7.336

7.354

7.372

7.594

7.613

7.777

7.799

8.493

8.514

8.734

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

21.247

61.675

76.683

77.000

77.318

109.524

114.208

115.203

120.693

122.591

124.112

126.728

130.076

133.823

135.294

136.980

138.177

156.305

158.463

166.290

129.4129.8130.2130.6f1 (ppm)

129.933

130.076

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

2.09

0.95

1.791.011.871.001.87

0.951.84

0.006

5.895

6.844

7.240

7.260

7.277

7.321

7.342

7.360

7.383

7.403

7.593

7.612

7.915

7.936

8.505

8.526

8.731

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

-0.131

61.918

76.682

77.000

77.319

109.819

114.221

115.315

120.727

124.250

128.476

128.884

134.930

139.544

156.278

158.482

165.268

128.0128.5129.0129.5f1 (ppm)

128.476

128.757

128.884

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

2.14

1.031.761.071.081.141.931.001.000.84

1.011.820.82

0.014

5.995

6.908

7.245

7.260

7.282

7.329

7.349

7.367

7.430

7.449

7.469

7.517

7.535

7.554

7.580

7.600

7.619

7.871

7.892

8.002

8.022

8.073

8.091

8.519

8.540

8.746

8.906

8.927

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

61.777

76.682

77.000

77.318

109.940

114.222

115.307

120.724

122.618

124.172

124.455

125.663

126.205

126.840

127.812

128.539

128.954

130.260

133.492

156.314

158.498

166.990

134.0135.0136.0137.0f1 (ppm)

133.492

133.795

135.180

137.024

124125126127128129f1 (ppm)

124.172

124.455

125.663

126.205

126.840

127.812

128.539

128.954

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.09

2.04

1.09

2.261.100.97

1.001.92

0.008

2.079

5.663

6.775

7.224

7.243

7.260

7.301

7.320

7.338

7.574

7.593

8.488

8.509

8.754

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

20.973

61.256

76.682

77.000

77.319

109.528

114.105

115.318

120.613

122.570

124.079

128.890

135.177

136.917

156.226

158.402

170.548

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

2.06

1.00

1.24

1.06

1.02

1.04

1.99

0.006

4.761

6.709

7.230

7.248

7.260

7.267

7.301

7.321

7.339

7.569

7.588

8.470

8.491

8.779

0102030405060708090100110120130140150160170180190200210f1 (ppm)

-0.019

58.004

76.683

77.000

77.317

110.194

113.708

115.506

120.899

122.857

124.242

129.171

136.797

139.721

155.874

158.729

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.033.00

2.04

2.04

0.97

4.074.394.132.16

2.04

0.017

3.719

3.871

4.407

5.552

6.119

7.005

7.023

7.042

7.057

7.075

7.094

7.112

7.132

7.150

7.233

7.260

7.277

7.297

7.362

7.382

7.400

7.412

7.432

7.507

7.525

7.538

7.557

7.934

7.953

0102030405060708090100110120130140150160170180190200210f1 (ppm)

22.683

29.730

30.002

56.209

76.683

77.000

77.318

100.492

108.656

109.239

112.015

119.111

119.484

119.639

120.575

127.003

129.582

133.125

137.300

137.603

139.718

166.155

119.0119.4119.8120.2120.6f1 (ppm)

119.111

119.484

119.639

119.861

120.575

129.55129.65129.75129.85f1 (ppm)

129.582

129.692

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

2.903.142.00

1.95

1.871.002.091.951.091.981.84

0.001

3.653

3.839

3.915

5.654

6.744

6.747

6.750

7.033

7.260

7.328

7.347

7.367

7.430

7.452

7.486

7.505

7.524

7.678

7.699

7.886

7.907

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

30.124

52.262

55.738

56.920

76.682

77.001

77.319

101.739

113.893

115.065

116.678

128.306

129.176

129.565

129.637

131.262

133.068

139.647

156.035

165.867

168.114

170.881

132.9133.1133.3133.5133.7f1 (ppm)

133.068

133.237

133.353

129.50129.60129.70129.80f1 (ppm)

129.565

129.637

Supporting InformationS1 Supporting Information Cobalt-Catalyzed C2α-acyloxylation of 2-Substituted...

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Transcript of Supporting InformationS1 Supporting Information Cobalt-Catalyzed C2α-acyloxylation of 2-Substituted...