Intramolecular vs intermolecular induction in the diastereoselective catalytic reduction of 17-oxo-steroids

被引：14

作者：

Reiners, I

Martens, J

Schwarz, S

Henkel, H

机构：

[1] UNIV OLDENBURG,FACHBEREICH CHEM,D-26129 OLDENBURG,GERMANY

[2] JENAPHANN GMBH,GESCHAFTSBEREICH FORSCH & ENTWICKLUNG,D-07745 JENA,GERMANY

来源：

TETRAHEDRON-ASYMMETRY | 1996年 / 7卷 / 06期

关键词：

D O I：

10.1016/0957-4166(96)00211-X

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The asymmetric reduction of enantiomerically pure steroid ketones was carried out by using oxazaborolidine catalysts with a variety of achiral or chiral ligands. The efficiency of chiral ligands (1,2-amino alcohols) as well as the effect of the stereogenic centers in the substrate on the catalytic asymmetric reduction were studied. It was found that the diastereoselectivity is mainly controlled by the absolute configuration of the chiral ligand. The reduction gave either the 17 alpha- or 17 beta-alcohol with high diastereomeric purity. This catalytic reduction represents a very practical solution to the problem of controlling C(17)-stereochemistry in synthesis of steroid compounds, Copyright (C) 1996 Elsevier Science Ltd

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页码：1763 / 1770

页数：8

相关论文

共 24 条

[1] ENANTIOSELECTIVE CATALYTIC BORANE REDUCTIONS OF ACHIRAL KETONES - SYNTHESIS AND APPLICATION OF NEW CATALYSTS PREPARED FROM (S)-TERT-LEUCINE AND (S)-AZETIDINECARBOXYLIC ACID [J].

BEHNEN, W ;

DAUELSBERG, C ;

WALLBAUM, S ;

MARTENS, J .

SYNTHETIC COMMUNICATIONS, 1992, 22 (15) :2143-2153

[2] A NEW PROCESS FOR THE GENERATION OF 1,3,2-OXAZABOROLIDINES, CATALYSTS FOR ENANTIOSELECTIVE SYNTHESIS [J].

COREY, EJ ;

LINK, JO .

TETRAHEDRON LETTERS, 1992, 33 (29) :4141-4144

[3] A NEW SYSTEM FOR CATALYTIC ENANTIOSELECTIVE REDUCTION OF ACHIRAL KETONES TO CHIRAL ALCOHOLS - SYNTHESIS OF CHIRAL ALPHA-HYDROXY ACIDS [J].

COREY, EJ ;

BAKSHI, RK .

TETRAHEDRON LETTERS, 1990, 31 (05) :611-614

[4] HIGHLY ENANTIOSELECTIVE BORANE REDUCTION OF KETONES CATALYZED BY CHIRAL OXAZABOROLIDINES - MECHANISM AND SYNTHETIC IMPLICATIONS [J].

COREY, EJ ;

BAKSHI, RK ;

SHIBATA, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (18) :5551-5553

[5] A STABLE AND EASILY PREPARED CATALYST FOR THE ENANTIOSELECTIVE REDUCTION OF KETONES - APPLICATIONS TO MULTISTEP SYNTHESES [J].

COREY, EJ ;

BAKSHI, RK ;

SHIBATA, S ;

CHEN, CP ;

SINGH, VK .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (25) :7925-7926

[6] ENANTIOSELECTIVE CATALYTIC BORANE REDUCTIONS OF ACHIRAL KETONES - SYNTHESIS AND APPLICATION OF NEW RIGID CATALYSTS PREPARED FROM (R)-PHENYLGLYCINE AND (S)-PHENYLALANINE [J].

DAUELSBERG, C ;

MARTENS, J .

SYNTHETIC COMMUNICATIONS, 1993, 23 (15) :2091-2099

[7] ASYMMETRIC BORON-CATALYZED REACTIONS [J].

DELOUX, L ;

SREBNIK, M .

CHEMICAL REVIEWS, 1993, 93 (02) :763-784

[8] ENANTIOSELECTIVE HYDROGENATION USING A RIGID BICYCLIC AMINOPHOSPHINE PHOSPHINITE LIGAND [J].

DOBLER, C ;

SCHMIDT, U ;

KRAUSE, HW ;

KREUZFELD, HJ ;

MICHALIK, M .

TETRAHEDRON-ASYMMETRY, 1995, 6 (02) :385-388

[9]

FARGE D, 1977, Patent No. 2635516

[10] ASYMMETRIC REDUCTION OF AROMATIC KETONES WITH CHIRAL ALKOXY-AMINE-BORANE COMPLEXES [J].

HIRAO, A ;

ITSUNO, S ;

NAKAHAMA, S ;

YAMAZAKI, N .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1981, (07) :315-317