Supporting information and Dihydroxypyrrolizidine · and Dihydroxypyrrolizidine Shruti Vandana...
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S1 Supporting information Stereoselective Approach to Indolizidine and Pyrrolizidine Alkaloids: Total Synthesis of (-)-Lentiginosine, (-)-epi-Lentiginosine and Dihydroxypyrrolizidine Shruti Vandana Kauloorkar, a Vishwajeet Jha, a Ganesh Jogdand b and Pradeep Kumar,* a . a Organic Chemistry Division, CSIR-National Chemical Laboratory (CSIR-NCL), Homi Bhabha Road, Pune – 411008, India. Fax +91-20-25902629; e-mail: [email protected] b NMR division, CSIR-National Chemical Laboratory (CSIR-NCL), Homi Bhabha Road, Pune – 411008, India. Table of contents 1. 1 H and 13 C spectra for compound 9 S3 2. 1 H and 13 C spectra for compound 10 S4 3. 1 H and 13 C spectra for compound 11 S5 4. 1 H and 13 C spectra for compound 16 S6 5. 1 H and 13 C spectra for compound 12 S7-S8 Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is © The Royal Society of Chemistry 2014
Transcript of Supporting information and Dihydroxypyrrolizidine · and Dihydroxypyrrolizidine Shruti Vandana...
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Supporting information
Stereoselective Approach to Indolizidine and Pyrrolizidine
Alkaloids: Total Synthesis of (-)-Lentiginosine, (-)-epi-Lentiginosine
and Dihydroxypyrrolizidine
Shruti Vandana Kauloorkar,a Vishwajeet Jha,a Ganesh Jogdandb and Pradeep Kumar,*a.
a Organic Chemistry Division, CSIR-National Chemical Laboratory (CSIR-NCL), Homi Bhabha
Road, Pune – 411008, India. Fax +91-20-25902629; e-mail: [email protected]
b NMR division, CSIR-National Chemical Laboratory (CSIR-NCL), Homi Bhabha Road, Pune –
411008, India.
Table of contents
1. 1H and 13C spectra for compound 9 S3
2. 1H and 13C spectra for compound 10 S4
3. 1H and 13C spectra for compound 11 S5
4. 1H and 13C spectra for compound 16 S6
5. 1H and 13C spectra for compound 12 S7-S8
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2014
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6. 1H and 13C spectra for compound 13 S9-S10
7. 1H and 13C spectra for compound 14 S11
8. 1H and 13C spectra for compound 15 S12
9. 1H and 13C spectra for compound 17 S13
10. 1H and 13C spectra for compound 3 S14
11. 1H and 13C spectra for compound 2 S15
12. 1H and 13C spectra for compound 4 S16
13. HRMS S17-S19
14. HPLC Profiles S20-S26
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Dibenzyl (R)-1-(1,8-dihydroxyoctan-4-yl)hydrazine-1,2-dicarboxylate (9):
OHNCbz
CbzHN
HO
S4
Dibenzyl 1-((2R,3S,4R)-8-((tert-butyldimethylsilyl)oxy)-1-ethoxy-2,3-dihydroxy-1-oxooctan-4-yl)hydrazine-1,2-dicarboxylate (10):
TBSO COOEt
NHN
OH
OHCbz
Cbz
S5
Dibenzyl 1-((2S,3R,4R)-8-((tert-butyldimethylsilyl)oxy)-1-ethoxy-2,3-dihydroxy-1-oxooctan-
4-yl)hydrazine-1,2-dicarboxylate (11) :
TBSO COOEt
NNH
OH
OHCbz
Cbz
S6
Dibenzyl 1-((2S,3R,4R)-7-((tert-butyldimethylsilyl)oxy)-1-ethoxy-2,3-dihydroxy-1-oxoheptan-4-yl)hydrazine-1,2-dicarboxylate (16):
TBSOCOOEt
NNH
OH
OHCbz
Cbz
S7
(3R,4S,5R)-5-(4-((tert-butyldimethylsilyl)oxy)butyl)-3,4-dihydroxypyrrolidin-2-one (12):
TBSO
HNO
OH
OH
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(3R,4S,5R)-5-(4-((tert-butyldimethylsilyl)oxy)butyl)-3,4-dihydroxypyrrolidin-2-one (12):
1HNMR in Acetone-d6:
TBSO
HNO
OH
OH
S9
(3S,4R,5R)-5-(4-((tert-butyldimethylsilyl)oxy)butyl)-3,4-dihydroxypyrrolidin-2-one (13):
TBSO
HNO
OH
OH
S10
(3S,4R,5R)-5-(4-((tert-butyldimethylsilyl)oxy)butyl)-3,4-dihydroxypyrrolidin-2-one (13):
1HNMR in Acetone-d6:
TBSO
HNO
OH
OH
S11
Dibenzyl 1-((2S,3S,4R)-1,2,3,8-tetrahydroxyoctan-4-yl)hydrazine-1,2-dicarboxylate (14):
HOOH
NCbz
HNCbz
OHOH
S12
Dibenzyl 1-((2R,3R,4R)-1,2,3,8-tetrahydroxyoctan-4-yl)hydrazine-1,2-dicarboxylate (15):
HOOH
NCbz
HNCbz
OHOH
S13
Dibenzyl 1-((2R,3R,4R)-1,2,3,7-tetrahydroxyheptan-4-yl)hydrazine-1,2-dicarboxylate (17):
HO OHNCbz
OH
OHCbzHN
S14
(1S,2S,8aR)- octahydroindolizine-1,2-diol (3):
N
OH
OH
S15
(1R,2R,8aR)-octahydroindolizine-1,2-diol (2):
NOH
OH
S16
(1R,2R,7aR)-hexahydro-1H-pyrrolizine-1,2-diol (4):
N
H OH
OH
S17
S18
S19
S20
Enantiomeric excess of compound 8a and 8b:
COOEt
NCbzCbzHN
TBSO
S21
S22
TBSOCOOEt
NCbz NH
Cbz
S23
S24
Diastereomeric ratio of compounds 10,11 and 16
S25
S26
