Supporting information and Dihydroxypyrrolizidine · and Dihydroxypyrrolizidine Shruti Vandana...
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
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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
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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
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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
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(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
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(3S,4R,5R)-5-(4-((tert-butyldimethylsilyl)oxy)butyl)-3,4-dihydroxypyrrolidin-2-one (13):
TBSO
HNO
OH
OH
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(3S,4R,5R)-5-(4-((tert-butyldimethylsilyl)oxy)butyl)-3,4-dihydroxypyrrolidin-2-one (13):
1HNMR in Acetone-d6:
TBSO
HNO
OH
OH
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Dibenzyl 1-((2S,3S,4R)-1,2,3,8-tetrahydroxyoctan-4-yl)hydrazine-1,2-dicarboxylate (14):
HOOH
NCbz
HNCbz
OHOH
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Dibenzyl 1-((2R,3R,4R)-1,2,3,8-tetrahydroxyoctan-4-yl)hydrazine-1,2-dicarboxylate (15):
HOOH
NCbz
HNCbz
OHOH
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Dibenzyl 1-((2R,3R,4R)-1,2,3,7-tetrahydroxyheptan-4-yl)hydrazine-1,2-dicarboxylate (17):
HO OHNCbz
OH
OHCbzHN
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(1S,2S,8aR)- octahydroindolizine-1,2-diol (3):
N
OH
OH
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(1R,2R,8aR)-octahydroindolizine-1,2-diol (2):
NOH
OH
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(1R,2R,7aR)-hexahydro-1H-pyrrolizine-1,2-diol (4):
N
H OH
OH
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S17
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Enantiomeric excess of compound 8a and 8b:
COOEt
NCbzCbzHN
TBSO
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S21
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TBSOCOOEt
NCbz NH
Cbz
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Diastereomeric ratio of compounds 10,11 and 16
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S25
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