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 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: pk.tripathi@ncl.res.in

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

S2

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

S3

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

S8

(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