Supporting Information

© Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2008

Synthetic Studies on (+)-Biotin, Part 11: Application of

Cinchona Alkaloid - Mediated Asymmetric Alcoholysis of

meso-Cyclic Anhydride in the Total Synthesis of (+)-Biotin

Hui-Fang Dai,[a] Wen-Xue Chen,[a] Lei Zhao ,[b] Fei Xiong,[b] Hao Sheng,[b

] and Fen-Er Chen*[a,b] a Fudan- DSM Joint Laboratory for Synthetic Method and Chiral Technology, Fudan University, Shanghai,

200433, P. R. China. b Institute of Biomedical Science, Fudan University, Shanghai, 200031, P. R. China.

Fax: +86(21)65643811. E-mail: rfchen@fudan.edu.cn

1H NMR (400 MHz, CDCl3): (4S, 5R)-1, 3-dibenzyl-2-oxo-5-

((3-phenylallyloxy) carbonyl)imidazolidine-4-carboxylic acid(4)

13C NMR (100 MHz, CDCl3): (4S, 5R)-1, 3-dibenzyl-2-oxo-5-((3-phenylallyloxy) carbonyl)imidazolidine-4-carboxylic acid(4)

IR: (4S, 5R)-1, 3-dibenzyl-2-oxo-5-((3-phenylallyloxy) carbonyl)

imidazolidine-4-carboxylic acid(4)

Chiral HPLC of enantiomeric excess of (4S, 5R)-1, 3-Dibenzyl-2-oxo-5- ((3-phenylallyloxy) carbonyl)imidazolidine-4-carboxylic acid(4)

1H NMR (400 MHz, CDCl3): (3aS, 6aR)-1, 3-dibenzyl-tetrahydro-1H-furo[3,4-d]imida

zole-2, 4-dione(6)

13C NMR (100 MHz, CDCl3): (3aS, 6aR)-1, 3-dibenzyl-tetrahydro-1H-furo-

[3,4-d]imida zole-2, 4-dione(6)

1H NMR (400 MHz, CDCl3): (3aS, 6aR)-1, 3-dibenzyl-tetrahydro-1H-thieno-

[3,4-d]-imidazole-2,4-dione(7)

13C NMR (100 MHz, CDCl3): (3aS, 6aR)-1, 3-dibenzyl-tetrahydro-1H-thieno-

[3,4-d]-imidazole-2,4-dione(7)

1H NMR (400 MHz, CDCl3): Ethyl 5-((3aS, 6aR)-1, 3-dibenzyl-4-hydroxy-

2-oxo-hexahydro-1H-thieno[3,4-d]imidazol-4-yl)pentanoate(8)

IR: Ethyl 5-((3aS, 6aR)-1, 3-dibenzyl-4-hydroxy-2-oxo-hexahydro-

1H-thieno[3,4-d]imidazol-4-yl)pentanoate(8)

1316:04:10

30-Apr-2008FDU Quattro Micro QAA1228080430-DHF-468-02

m/z150 175 200 225 250 275 300 325 350 375 400 425 450 475 500 525 550 575 600 625 650 675 700 725 750 775 800

%

0

100

080430-DHF-468-03 136 (3.638) 1: Scan ES+ 7.53e5323.1

293.3

158.3

167.1

245.3171.5

182.2

215.2

187.2225.1

292.9

267.2

315.4

469.4323.7

345.4344.9

324.4

387.2

365.8437.0410.0

468.9

493.1

493.9555.7

515.2545.3

671.6641.0574.7

625.1596.4

709.6681.3

764.1744.9 771.6 797.2

MS(ESI): Ethyl 5-((3aS, 6aR)-1, 3-dibenzyl-4-hydroxy-2-oxo-hexahydro-

1H-thieno[3,4-d]imidazol-4-yl)pentanoate(8)

1H NMR (400 MHz, CDCl3): Ethyl 5-((3aS, 4S, 6aR)-1, 3-dibenzyl-2-

oxo-hexahydro-1H –thieno[3, 4-d]imidazol-4-yl)pentanoic (9)

13C NMR (100 MHz, CDCl3): Ethyl 5-((3aS, 4S, 6aR)-1, 3-dibenzyl-2-oxo-

hexahydro-1H –thieno[3, 4-d]imidazol-4-yl)pentanoic (9)

2D NOESY : Ethyl 5-((3aS, 4S, 6aR)-1, 3-dibenzyl-2-oxo-hexahydro-1H –thieno

[3, 4-d]imidazol-4-yl)pentanoic (9)

IR: Ethyl 5-((3aS, 4S, 6aR)-1, 3-dibenzyl-2-oxo-hexahydro-1H –thieno[3, 4-d]

imidazol-4-yl)pentanoic (9)

1018:29:30

09-Jan-2008FDU Quattro Micro QAA1228080109-DHF-450

m/z160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600

%

0

100

080109-DHF-450 152 (3.060) Cm (150:164) 1: Scan ES+ 3.46e7453.3

289.2

261.2172.2

157.1

233.2

182.2 205.1

184.3

186.3 218.1 246.2 274.2

407.3311.2

290.4 361.3315.2 352.2379.3 397.1

425.4

408.6 451.3

454.7

455.6475.3

519.3476.6 507.2 537.3 566.5559.1 599.0588.8

MS(ESI): Ethyl 5-((3aS, 4S, 6aR)-1, 3-dibenzyl-2-oxo-hexahydro-1H –thieno

[3, 4-d]imidazol-4-yl)pentanoic (9)

1H NMR (400 MHz, CDCl3): (+)-Biotin (1)

13C NMR (100 MHz, CDCl3): (+)-Biotin (1)

TEM photograph of the Pd nanoparticles immobilized on anion exchange resin D296 (Pd@D296)