Studies on the asymmetric total synthesis of d-biotin(V)

被引：0

作者：

Chen, FE ^{[1
]}

Fu, H ^{[1
]}

Meng, G ^{[1
]}

Luo, YF ^{[1
]}

Yan, MG ^{[1
]}

机构：

[1] Fudan Univ, Dept Chem, Shanghai 200433, Peoples R China

来源：

CHEMICAL JOURNAL OF CHINESE UNIVERSITIES-CHINESE | 2002年 / 23卷 / 06期

关键词：

d-biotin; vitamin H; steroselective reduction; catalytic hydrogen transfer; asymmetric synthesis;

D O I：

暂无

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

An efficient, high-yielding and stereoselective synthesis of d-biotin(6) is described. The stereoselective reduction of the known (3aS, 6aR) -1,3-dibenzyl-tetrahydro-4H-thieno-[3,4-d]imidazol- 2,4(1H)-dione(1) with diisobutylaluminum hydride(DIBAL-H) in toluene gave(3aS, 4S,6aR)-1,3-dibenzyl-4-hydroxy-tetrahydro-1H-thieno-[3,4-d]imidazol-2 (3H)-one (2) in 91% yield with 99.7% e. e.. Alcohol 2 was directly converted into 3aS, 4S, 6aR)-phosphonium salt 3 upon reaction with triphenylphosphine hydrogen tetrafluoroborate. Condensation of the corresponding ylide with 4-formylbutric acid afforded unsaturated acid 4. Catalytic hydrogen transfer hydrogenation of compound 4 with Pd-D297 resin/ammonium formate system led stereoselectively to(3aS, 4S, 6aS)-dibenzylbiotion(5), which was debenzylated by treatment with orthophospaoric acid in the presence of phenol to yield d-biotin(6). The overall yield of d-biotin was 42% from thiolactone 1.

引用

页码：1060 / 1064

页数：5

共 18 条

[1] PREPARATION OF (3A-ALPHA,6A-ALPHA)-1,3-DIBENZYLHEXAHYDRO-1H-THIENO[3,4-D]-IMIDAZOL-2(3H)-ONE - A KEY BIOTIN INTERMEDIATE
BATES, HA
SMILOWITZ, L
LIN, J
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1985, 50 (06) : 899 - 901
[2] SYNTHESIS OF (+)-BIOTIN - EFFICIENT RESOLUTION OF KEY INTERMEDIATES
BIHOVSKY, R
BODEPUDI, V
[J]. TETRAHEDRON, 1990, 46 (23) : 7667 - 7676
[3] Chen FE, 2001, CHEM J CHINESE U, V22, P1141
[4] Chen FE, 2000, SYNTHESIS-STUTTGART, P2004
[5] CHEN FE, 1995, ACTA PHARMACOL SINIC, V30, P824
[6] CHEN FE, 1999, ION EXCHANGE ADSORPT, V15, P572
[7] CHEN FE, 1999, ACTA PHARMACOL SINIC, V24, P827
[8] CIARK DA, 1977, SYNTHESIS-STUTTGART, P628
[9] HARPER DC, 1973, CHEM IND-LONDON, P587
[10] HOLICK W, 1986, Patent No. 154225

← 1 2 →