ePaper |Suvarna Vartha | Hyderabad & Kurnool District Edition | 07-03-2012
revised Supporting informationPerali Ramu Sridhar*, Kalapati Seshadri and Gadi Madhusudhan Reddy...
Transcript of revised Supporting informationPerali Ramu Sridhar*, Kalapati Seshadri and Gadi Madhusudhan Reddy...
1
SUPPORTING INFORMATION
Stereoselective Synthesis of Sugar Fused β-Disubstituted γ-butyro-lactones: C-Spiro-glycosides from 1,2-Cyclopropane-
-carboxylated Sugars
Perali Ramu Sridhar*, Kalapati Seshadri and Gadi Madhusudhan Reddy
School of Chemistry, University of Hyderabad, Hyderabad-500 046, India
Email : [email protected]
Table of Contents Page No.
General methods 2
General Procedures 2-3
Spectral Data 3-8
Spectras 7-118
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General Methods: All reactions are performed in oven-dried apparatus. Reaction
mixtures were stirred magnetically unless otherwise stated. All the products were
characterised by using NMR. Commercial grade solvents were distilled prior to use.
Dichlormethane, dimethyl formamide and methanol were intially dried and stored
over 4 A0 molecular sieves. 1H and 13C NMR spectra were recorded over 500 MHz
or 400 MHz and 125 MHz or 100 MHz respectively. Coupling constants are reported
in Hz. CDCl3 (0.03% TMS) was used for recording NMR spectra.
General Procedures and Data
General experimental procedure for the preparation of 1,2-
cyclopropanecarboxylates:
To a stirred suspension of glucal (1.0 mmol) and Rh2(OAc)4 (0.02 mmol) in
anhydrous CH2Cl2 (2 mL) was added dropwise, over a period of 1 h, a solution of
methyl diazoacetate (3 mmol) in CH2Cl2 (10 mL). After cessation of the nitrogen
evolution (5-10 min), the reaction mixture was concentrated in vacuo and the
remaining residue was purified by silica gel column chromatography (eluent: 10-30%
EtOAc in light petroleum) to give the desired 1,2-cyclopropanecarboxylate adduct.
General experimental procedure for NBS mediated ring opening of 1,2-
cyclopropanecarboxylate:
To a stirred solution of 1,2-cyclopropanecarboxylate (0.5 mmol) in 1,4-dioxane:water
(5 mL (2:1)) was added N-bromosuccinimide (0.6 mmol) and the stirring was
continued until the reaction mixture showed the absence of starting material on TLC.
The reaction mixture was then concentrated to half its volume in vacuo and extracted
with CH2Cl2 (2 x 10 mL). The combined extracts were dried over anhydrous Na2SO4,
filtered and concentrated. Purification by column chromatography over silica gel
using EtOAc:hexane provided the bromohydrin as color less gum in 65-81% yield.
General experimental procedure for the K2CO3 mediated one-pot reaction:
To a stirred solution of bromohydrin (0.25 mmol) in CH3OH (2 mL) under nitrogen
was added K2CO3 (0.50 mmol) at 25 0C. The reaction mixture was stirred for a period
of 6 h. CH3OH was evaporated, and the reaction mixture was diluted with CH2Cl2 (20
mL) and washed with 1% HCl (10 mL) and water (10 mL). The organic layer was
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dried over anhydrous Na2SO4 and concentrated. Column chromatography of the crude
product with EtOAc : hexane afforded the pure spirocyclic lactol as a color less gum
in 72-92% yield.
General experimental procedure for dehydroxylation:
To a stirred solution of spiro lactol (0.2 mmol) in CH2Cl2 at 0 oC was added triethyl
silane (0.8 mmol) and trifluoroacetic acid (0.4 mmol) dropwise respectively and
continued stirring while allowing the reaction to 25 oC. After completion of reactin (2-
3 h) solvent was evaporated and the crude product was purified by colum
chromatography over silicagel using EtOAc:hexane to afford pure spirolactone in 88-
94% yield.
Compound 20 and Compound 24: 1H NMR
(CDCl3, 400 MHz): δ 7.26-7.43 (m, 10H),
4.79 (s, 2H), 4.60 (s, 2H), 4.09 (s, 1H), 3.97
(d, 1H, J = 6.8 Hz), 3.86 (dd, 1H, J = 5.2 Hz,
J = 6.4 Hz), 3.67 (s, 3H), 3.54 (dd, 1H, J = 3.2 Hz, J = 10.4 Hz), 3.43-3.47 (m, 1H),
2.10 (t, 1H, J = 6.4 Hz), 1.60 (d, 1H, J = 6.4 Hz). 13C NMR (CDCl3, 100 MHz): δ
171.5, 138.0, 137.8, 128.3, 128.2, 128.1, 127.7, 127.6, 127.5, 127.4, 127.3, 73.4, 72.0,
71.2, 70.9, 62.9, 58.3, 51.7, 26.6, 25.4. Low-resolution MS (EI): m/z: 368 (M+).
Compound 33 (major diastereomer): 1H NMR (CDCl3, 400
MHz): δ 7.29-7.39 (m, 10H), 4.68 (d, 1H, J = 12 Hz), 4.60 (d,
1H, J = 12 Hz), 4.58 (d, 1H, J = 12 Hz), 4.51 (d, 1H, J = 12
Hz), 4.01 (dd, 1H, J = 1.6 Hz, J = 7.2 Hz), 3.95 (d, 1H, J = 2
Hz), 3.75 (dd, 1H, J = 1.6 Hz, J = 12 Hz), 3.69 (s, 3H), 3.49-3.50 (m, 1H), 2.30 (dd,
1H, J = 2 Hz, J = 6.4 Hz), 1.93 (dd, 1H, J = 6.4 Hz, J = 7.2 Hz). 13C NMR (CDCl3,
100 MHz): δ 172.5, 137.7, 128.5, 128.4, 127.9, 127.8, 127.7, 74.4, 71.6, 70.9, 70.4,
62.3, 58.7, 51.8, 24.4, 23.9. Low-resolution MS (EI): m/z: 368 (M+).
Compound 9: 1H NMR (CDCl3, 400 MHz): δ 7.26-7.29 (m,
15H), 4.51-4.62 (m, 6H), 4.12-4.17 (m, 2H), 4.04-4.07 (m,
1H), 3.76-3.85 (m, 2H), 3.54-3.69 (m, 4H), 1.99 (ddd, 1H, J =
OOH
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OBn
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BnO
OBn
COOMe
20 24
and
O
BnO
OBn
COOMe
33 (major product)
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3.2 Hz, J = 7.2 Hz, J = 15.2 Hz), 1.89 (ddd, 1H, J = 3.6 Hz, J = 7.2 Hz, J = 15.2 Hz). 13C NMR (CDCl3, 100 MHz): δ 137.8, 137.7, 137.6, 128.5, 128.4, 127.9, 127.9, 127.8,
127.8, 127.7, 127.7, 85.7, 85.7, 83.5, 79.6, 73.4, 72.7, 72.4, 69.6, 66.0, 58.8, 34.7.
Low-resolution MS (EI): m/z: 478 (M+).
Compound 10: 1H NMR (CDCl3, 400 MHz): δ 9.87 (s, 1H),
7.22-7.38 (m, 15H), 4.41-4.58 (m, 7H), 4.10 (d, 1H, J = 1.6
Hz), -4.08 (t, 1H, J = 2 Hz), 2H), 3.56-3.68 (m, 5H), 3.02 (d,
2H, J = 10.8 Hz). 13C NMR (CDCl3, 100 MHz): δ 204.1,
170.6, 137.9, 137.0, 136.9, 128.5, 128.4, 128.3, 128.0, 127.8, 129.7, 127.7, 127.6,
89.5, 84.7, 83.3, 81.5, 73.1, 72.6, 71.4, 71.1, 69.7, 51.9, 38.9. Low-resolution MS
(EI): m/z: 504 (M+).
Compound 11: 1H NMR (CDCl3, 400 MHz): δ 7.25-7.41 (m,
15H), 4.52-4.64 (m, 5H), 4.45 (d, 1H, J = 12 Hz), 4.34 (d, 1H, J
= 10 Hz), 4.20-4.23 (m, 2H), 4.11 (t, 1H, J = 3.2 Hz), 3.92 (d,
1H, J = 2.8 Hz), 3.50-3.59 (m, 2H), 2.97 (d, 1H, J = 18.4 Hz),
2.69 (d, 1H, J = 18.4 Hz). 13C NMR (CDCl3, 100 MHz): δ 175.1, 137.8, 137.4, 137.0,
128.7, 128.6, 128.4, 128.2, 128.1, 127.8, 129.8, 127.7, 87.2, 84.2, 82.6, 81.9, 75.7,
73.4, 72.0, 70.0, 35.8. Low-resolution MS (EI): m/z: 475 (M++1).
Compound 15: 1H NMR (CDCl3, 400 MHz): δ 7.28-7.39 (m,
15H), 4.73 (d, 1H, 11.6 Hz), 4.72 (d, 1H, J = 11.6 Hz), 4.63 (d,
1H, J = 11.6 Hz), 4.58 (d, 1H, J 12 Hz), 4.51 (d, 1H, J = 12 Hz),
4. 48 (d, 1H, J = 12 Hz), 4.28 (d, 1H, J = 10 Hz), 4.19-4.23 (m,
1H), 4.14 (t, 1H, J = 3.6 Hz), 4.11 (d, 1H, J = 10 Hz), 3.82 (d, 1H, J = 3.6 Hz), 3.73
(dd, 1H, J = 6.4 Hz, J = 9.2 Hz), 3.61 (dd, 1H, J = 6 Hz, J = 9.6 Hz), 3.26 (d, 1H, J =
18.4 Hz), 2.56 (d, 1H, J = 18.4 Hz). 13C NMR (CDCl3, 100 MHz): δ 176.2, 137.9,
137.6, 136.7, 128.6, 128.4, 127.7, 127.4, 84.6, 80.5, 78.9, 75.8, 75.7, 73.7, 73.5, 72.8,
68.5, 37.4. Low-resolution MS (EI): m/z: 475 (M++1).
Compound 19: 1H NMR (CDCl3, 400 MHz): δ 7.28-7.36 (m, 10H),
4.69 (d, 1H, J = 12 Hz), 4.57 (s, 1H), 4.56 (s, 1H), 4.52 (d, 1H, J =
12 Hz), 4.32 (d, 1H, J = 10 Hz), 4. 18 (d, 1H, J = 10 Hz), 4.11-4.13
O
CHO
BnO OBn
BnO
10
O
OMe
OO
BnO OBn
BnO
O
11
OO
BnO OBn
BnO
O
15
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
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(m, 1H), 3.89 (d, 1H, J = 2.8 Hz), 3.77 (dd, 1H, J = 2.8 Hz, J = 4 Hz), 2.99 (d, 1H, J
= 18 Hz), 2.64 (d, 1H, J = 18 Hz), 1.33 (d, 3H, J = 6.4 Hz). 13C NMR (CDCl3, 100
MHz): δ 175.0, 137.3, 137.0, 128.7, 128.6, 128.2, 128.1, 127.8, 129.6, 127.5, 87.4,
86.9, 84.9, 78.8, 75.9, 72.2, 72.1, 36.2, 20.2. Low-resolution MS (EI): m/z: 369
(M++1).
Compound 23 and Compound 27: 1H NMR
(CDCl3, 400 MHz): δ 7.31-7.38 (m, 10H), 4.77 (d,
1H, J = 12 Hz), 4.64 (d, 1H, J = 12 Hz), 4.56 (d,
1H, J = 12 Hz), 4.51 (d, 1H, J = 12 Hz), 4.24 (d,
1H, J = 10 Hz), 4.16 (d, 1H, J = 10 Hz), 4.07 (ddd, 1H, J = 1.2 Hz, J = 5.6 Hz, J =
10 Hz), 4.02 (d, 1H, J = 1.2 Hz), 3.98 (dd, 1H, J = 4 Hz, J = 10.8 Hz), 3.72 (d, 1H, J
= 4.4 Hz), 3.22 (d, 1H, J = 18.4 Hz), 2.51 (d, 1H, J = 18.4 Hz). 13C NMR (CDCl3,
100 MHz): δ 176.0, 137.5, 136.9, 128.6, 128.5, 128.3, 127.9, 129.8, 127.6, 84.7, 79.4,
75.3, 74.9, 72.5, 71.8, 70.6, 36.0. Low-resolution MS (EI): m/z: 355 (M++1).
Compound 32 (major Diastereomer): 1H NMR (CDCl3, 400
MHz): δ 7.28-7.42 (m, 10H), 4.69 (d, 1H, J = 11.2 Hz), 4.57 (s,
1H), 4.56 (s, 1H), 4.46 (d, 1H, J = 11.2 Hz), 4.35 (d, 1H, J = 10
Hz), 4.21 (d, 1H, J = 10 Hz), 4.16 (dd, 1H, J = 3.6 Hz, J = 7.6
Hz), 4.12 (dd, 1H, J = 2.0 Hz, J = 3.6 Hz), 3.89 (d, 1H, J = 2.0 Hz), 3.74-3.77 (m,
1H), 3.64-3.67 (m, 1H), 2.95 (d, 1H, J = 18.2 Hz), 2.67 (d, 1H, J = 18.2 Hz), 2.06 (bs,
1H). 13C NMR (CDCl3, 100 MHz): δ 174.7, 137.0, 136.6, 128.8, 128.7, 128.4, 128.3,
128.0, 127.7, 87.8, 83.9, 89.9, 82.1, 75.3, 72.4, 72.0, 62.8, 35.7. Low-resolution MS
(EI): m/z: 384 (M+).
Compound 36 (major diastereomer): 1H NMR (CDCl3, 400 MHz):
δ 7.32-7.44 (m, 10H), 4.71 (d, 1H, J = 12 Hz), 4.58 (d, 1H, J =
11.6 Hz), 4.56 (d, 1H, J = 12 Hz), 4.51(d, 1H, J = 12 Hz), 4.35 (d,
1H, J = 6.0 Hz), 4.25 (d, 1H, J = 6.0 Hz), 4.15-4.18 (m, 1H), 4.09
(dd, 1H, J = 4.4 Hz, J = 10.0 Hz), 4.00 (bs, 1H), 3.92 (bs, 1H), 3.00 (d, 1H, J = 18.0
Hz), 2.61 (d, 1H, J = 18.0 Hz). 13C NMR (CDCl3, 100 MHz): δ 175.0, 137.2, 137.0,
128.7, 128.6, 128.3, 127.8, 127.6, 87.3, 84.2, 81.7, 76.0, 72.4, 71.8, 70.9, 35.1. Low-
resolution MS (EI): m/z: 355 (M++1).
OO
BnO OBn
HO
O
32
OO
BnO OBn
O
23
OO
BnO OBn
O
27
and
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Compound 38: 1H NMR (CDCl3, 500 MHz): δ 6.97 (dd, 1H, J
= 1.5 Hz, J = 2.5 Hz), 4.45 (s, 1H), 3.91 (dd, 1H, J = 4.5 Hz, J
= 11.5 Hz), 3.70-3.74 (m, 4H), 3.47-3.57 (m, 2H), 2.81 (dt, 1H,
J = 3.5 Hz, J = 19.0 Hz), 2.15 (d, 1H, J = 14.5 Hz), 1.90-1.95
(dt, 1H, J = 4.5 Hz, J = 13 Hz), 1.70-1.77 (m, 1H), 1.36 (d, 1H, J = 12 Hz). 13C NMR
(CDCl3, 125 MHz): δ 165.6, 164.4, 138.4, 129.0, 74.7, 69.3, 68.0, 51.7, 31.8, 28.2,
19.0. Low-resolution MS (EI): m/z: 226 (M+).
Compound 41: 1H NMR (CDCl3, 400 MHz): δ 7.26-7.35 (m,
10H), 6.97 (dd, 1H, J = 6.8 Hz, J = 16.4 Hz), 6.09 (d, 1H, J
= 15.6 Hz), 4.62 (d, 1H, J = 11.6 Hz), 4.52 (s, 2H), 4.40 (d,
1H, J = 11.6 Hz), 4.09 (t, 1H, J = 6 Hz), 3.91 (m, 1H), 3.76
(s, 3H), 3.59 (d, 2H, J = 4.8 Hz), 2.43 (bs, 1H). 13C NMR (CDCl3, 100 MHz): δ 166.2,
144.9, 137.7, 137.6, 128.4, 127.8, 123.8, 78.6, 73.5, 72.2, 71.6, 70.3, 51.7. Low-
resolution MS (EI): m/z: 357 (M++1).
Compound 48 (major diastereomer): 1H NMR (CDCl3, 400
MHz): δ 5.49 (bs, 1H), 4.43-4.45 (m, 1H), 4.18 (dd, 1H, J = 6.0
Hz, J = 8.4 Hz), 3.88 (dd, 1H, J = 2 Hz, J = 11.2 Hz), 3.80 (dd,
1H, J = 4.0 Hz, J = 11.2 Hz), 3.62-3.65 (m, 1H), 3.02 (d, 1H, J =
18.0 Hz), 2.65 (d, 1H, J = 18 Hz), 2.14-2.21 (m, 2H), 1.37 (s, 3H),
1.27 (s, 3H), 0.93 (s, 9H), 0.10 (s, 6H). 13C NMR (CDCl3, 100 MHz): δ 171.7, 109.5,
102.2, 76.0, 73.7, 70.0, 69.5, 62.6, 40.4, 31.6, 27.7, 25.8, 25.3, 18.3, -5.2, -5.3. Low-
resolution MS (EI): m/z: 388 (M+).
O
O O
COOMe
38
O O
O
OHOO
TBSO
48
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
7
1 HNMR,400MHz,CDCl 3
O
BnO
OBn
BnO
COOMe
OH
Br
7
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
8
13CNMR,100MHz,CDCl 3
O
BnO
OBn
BnO
COOMe
OH
Br
7
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
9
1HNMR,400MHz,CDCl 3
OO
BnO
OBn
BnO
O OH
8
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
10
13 CNMR,100MHz,CDCl 3
OO
BnO
OBn
BnO
O
OH
8
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
11
13 CDEPT,100MHz,CDCl 3
OO
BnO
OBn
BnO
O OH
8
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
12
1HNMR,400MHz,CDCl 3
OOH
BnO
OBn
BnO
OH
9
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
13
13 CNMR,100MHz,CDCl 3
OOH
BnO
OBn
BnO
OH
9
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
14
13 CDEPT,100MHz,CDCl 3
OOH
BnO
OBn
BnO
OH
9
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
15
ppm
2.0
2.5
3.0
3.5
4.0
4.5
5.0
ppm
2.0
2.5
3.0
3.5
4.0
4.5
5.0
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
16
NOESY,400MHz,CDCl 3
OOH
BnO
OBn
BnO
OH
9
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
17
1 HNMR,400MHz,CDCl 3
O
CHO
BnO
OBn
BnO
10
O
OMe
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
18
13 CNMR,100MHz,CDCl 3
O
CHO
BnO
OBn
BnO
10
O
OMe
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
19
13 CDEPT,100MHz,CDCl 3
O
CHO
BnO
OBn
BnO
10
O
OMe
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
20
1HNMR,400MHz,CDCl 3
OO
BnO
OBn
BnO
O
11
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
21
13 CNMR,100MHz,CDCl 3
OO
BnO
OBn
BnO
O
11
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
22
13 CDEPT,100MHz,CDCl 3
OO
BnO
OBn
BnO
O
11
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
23
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
24
NOESY,400MHz,CDCl 3
OO
BnO
OBn
BnO
O
11
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
25
O
BnO
OBn
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COOMe
OH
Br
1 HNMR,400MHz,CDCl 3
13
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
26
O
BnO
OBn
BnO
COOMe
OH
Br
13CNMR,100MHz,CDCl 3
13
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
27
1HNMR,400MHz,CDCl 3
OO
BnO
OBn
BnO
O OH
14
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
28
13 CNMR,100MHz,CDCl 3
OO
BnO
OBn
BnO
O
OH
14
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
29
13 CDEPT,100MHz,CDCl 3
OO
BnO
OBn
BnO
O OH
14
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
30
1HNMR,400MHz,CDCl 3
OO
BnO
OBn
BnO
O
15
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
31
13 CNMR,100MHz,CDCl 3
OO
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OBn
BnO
O
15
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
32
13 CDEPT,100MHz,CDCl 3
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BnO
OBn
BnO
O
15
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
33
ppm
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
ppm
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
34
ppm
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
ppm
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
NOESY,400MHz,CDCl 3
OO
BnO
OBn
BnO
O
15
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
35
1HNMR,400MHz,CDCl 3
17
O
BnO
OBn
COOMe
OH
Br
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
36
13 CNMR,100MHz,CDCl 3
17
O
BnO
OBn
COOMe
OH
Br
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
37
1HNMR,400MHz,CDCl 3
OO
BnO
OBn
O OH
18
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
38
13 CNMR,100MHz,CDCl 3
OO
BnO
OBn
O OH
18
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
39
13 CDEPT,100MHz,CDCl 3
OO
BnO
OBn
O OH
18
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
40
1HNMR,400MHz,CDCl 3
OO
BnO
OBn
O
19
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
41
13 CNMR,100MHz,CDCl 3
OO
BnO
OBn
O
19
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
42
13 CDEPT,100MHz,CDCl 3
OO
BnO
OBn
O
19
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
43
ppm
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
ppm
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
44
ppm
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
ppm
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
NOESY,400MHz,CDCl 3
OO
BnO
OBn
O
19
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
45
1HNMR,400MHz,CDCl 3
O
BnO
OBn
COOMe
20
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
46
13 CNMR,100MHz,CDCl 3
O
BnO
OBn
COOMe
20
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
47
13 CDEPT,100MHz,CDCl 3
O
BnO
OBn
COOMe
20
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
48
1HNMR,400MHz,CDCl 3
O
BnO
OBn
COOMe
OH
Br
21
H
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
49
13 CNMR,100MHz,CDCl 3
O
BnO
OBn
COOMe
OH
Br
21
H
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
50
13 CDEPT,100MHz,CDCl 3
O
BnO
OBn
COOMe
OH
Br
21
H
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
51
1HNMR,400MHz,CDCl 3
OO
BnO
OBn
O OH
22
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
52
13 CNMR,100MHz,CDCl 3
OO
BnO
OBn
O OH
22
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
53
13 CDEPT,100MHz,CDCl 3
OO
BnO
OBn
O OH
22
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
54
1 HNMR,500MHz,CDCl 3
OO
BnO
OBn
O
23
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
55
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
56
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
57
ppm
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
ppm
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
1 H-1 HCOSY,500MHz,CDCl 3
OO
BnO
OBn
O
23
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
58
ppm
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
ppm
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
59
1HNMR,400MHz,CDCl 3
O
BnO
OBn
COOMe
24
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
60
13 CNMR,100MHz,CDCl 3
O
BnO
OBn
COOMe
24
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
61
13 CDEPT,100MHz,CDCl 3
O
BnO
OBn
COOMe
24
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
62
1 HNMR,400MHz,CDCl 3
O
BnO
OBn
COOMe
OH
BrH
25
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
63
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
64
1HNMR,400MHz,CDCl 3
OO
BnO
OBn
O OH
26
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
65
13 CNMR,100MHz,CDCl 3
OO
BnO
OBn
O OH
26
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
66
1HNMR,400MHz,CDCl 3
OO
BnO
OBn
O
27
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
67
13 CNMR,100MHz,CDCl 3
OO
BnO
OBn
O
27
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
68
ppm
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
ppm
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
69
NOESY,400MHz,CDCl 3
OO
BnO
OBn
O
27
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
70
O
BnO
OBn
HO
COOMe
OH
Br
1HNMR,400MHz,CDCl 3
29
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
71
O
BnO
OBn
HO
COOMe
OH
Br
13 CNMR,100MHz,CDCl 3
29
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
72
O
BnO
OBn
TBSO
COOMe
OH
Br
1HNMR,400MHz,CDCl 3
30
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
73
O
BnO
OBn
TBSO
COOMe
OH
Br
13CNMR,100MHz,CDCl 3
30
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
74
1HNMR,400MHz,CDCl 3
OO
BnO
OBn
TBSO
O
OH
31
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
75
13 CNMR,100MHz,CDCl 3
OO
BnO
OBn
TBSO
O
OH
31
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
76
1 HNMR,400MHz,CDCl 3
OO
BnO
OBn
O
32
HO
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
77
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
78
13CDEPT,100MHZ,CDCl 3
OO
BnO
OBn
O
32
HO
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
79
ppm
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
ppm
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
80
ppm
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
ppm
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
81
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
82
200
190
180
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0ppm
23.9924.4825.7026.03
51.8251.9458.7662.3062.3566.0170.3970.8970.9371.6172.7974.4275.4076.5376.8077.1277.3277.44
127.69127.71127.75127.80127.84127.87127.92128.45128.52128.55129.74137.79137.81138.18
171.84172.56
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
83
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
ppm
23.9924.4825.7026.03
51.8251.9558.7662.3062.3666.0170.3870.8970.9371.6072.7974.4175.4076.52
127.69127.72127.76127.80127.84127.87127.92128.45128.52128.55
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
84
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
85
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
86
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
87
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
88
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
89
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
90
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
91
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
92
ppm
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
ppm
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
93
ppm
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
ppm
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
94
1 HNMR,400MHz,CDCl 3
O
COOMe
O
37
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
95
13CNMR,100MHz,CDCl 3
O
COOMe
O
37
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
96
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
97
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
98
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
99
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
100
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
101
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
102
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
103
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
104
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
105
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
106
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
107
13 CNMR,100MHZ,CDCl 3
BnO
COOMe
OH OBn
41
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
108
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
109
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
110
1 HNMR,400MHz,CDCl 3
O
O
O
TBSO
COOMe
45
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
111
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
112
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
113
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
114
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
115
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
116
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
117
13CNMR,100MHz,CDCl 3
OOO OH
OO
TBSO
48
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
118
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011