NOVEL METHOD FOR STEREOSPECIFIC GENERATION OF NATURAL C-17 STEREOCHEMISTRY AND EITHER C-20 EPIMER IN STEROID SIDE-CHAINS BY PALLADIUM-CATALYZED HYDROGENOLYSIS OF C-17 AND C-20 ALLYLIC CARBONATES

被引：25

作者：

MANDAI, T

MATSUMOTO, T

KAWADA, M

TSUJI, J

机构：

[1] Department of Applied Chemistry, Okayama University of Science, 700, Ridai-cho, Okayama, Japan

来源：

TETRAHEDRON | 1994年 / 50卷 / 02期

关键词：

D O I：

10.1016/S0040-4020(01)80769-9

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The allylic alcohol, obtained by the reaction of C-17-keto steroid with isopropenyllithium, was converted to carbonate. Its hydrogenolysis with triethylammonium formate affords C-17 beta-isopropenyl group. Steroid side chain units were introduced by the reaction of C-20 keto steroid with (E) and (Z) alkenyl lithiums. The natural epimer at C-20 in steroid side-chains was generated stereospecifically by the palladium-catalyzed hydrogenolysis with triethylammonium formate of C-20 (Z) allylic carbonates, and the unnatural configuration was generated by the C-20 (E) allylic carbonate.

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页码：475 / 486

页数：12

相关论文

共 51 条

[1] EVIDENCE OF THE FORMATION OF ZEROVALENT PALLADIUM FROM PD(OAC)2 AND TRIPHENYLPHOSPHINE [J].

AMATORE, C ;

JUTAND, A ;

MBARKI, MA .

ORGANOMETALLICS, 1992, 11 (09) :3009-3013

[2] STEREOSELECTIVE INTRODUCTION OF STEROID SIDE-CHAINS AT C(17) AND C(20) [J].

BATCHO, AD ;

BERGER, DE ;

DAVOUST, SG ;

WOVKULICH, PM ;

USKOKOVIC, MR .

HELVETICA CHIMICA ACTA, 1981, 64 (05) :1682-1687

[3] C-20 STEREOSPECIFIC INTRODUCTION OF A STEROID SIDE-CHAIN [J].

BATCHO, AD ;

BERGER, DE ;

USKOKOVIC, MR ;

SNIDER, BB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (05) :1293-1295

[4] 20-EPI-VITAMIN-D3 ANALOGS - A NOVEL CLASS OF POTENT REGULATORS OF CELL-GROWTH AND IMMUNE-RESPONSES [J].

BINDERUP, L ;

LATINI, S ;

BINDERUP, E ;

BRETTING, C ;

CALVERLEY, M ;

HANSEN, K .

BIOCHEMICAL PHARMACOLOGY, 1991, 42 (08) :1569-1575

[5] PALLADIUM-CATALYZED REDUCTION OF ENOL TRIFLATES TO ALKENES [J].

CACCHI, S ;

MORERA, E ;

ORTAR, G .

TETRAHEDRON LETTERS, 1984, 25 (42) :4821-4824

[6] (2,3)-WITTIG SIGMATROPIC REARRANGEMENTS IN STEROID-SYNTHESIS - NEW STEREOCONTROLLED APPROACH TO STEROIDAL SIDE-CHAINS AT C-20 [J].

CASTEDO, L ;

GRANJA, JR ;

MOURINO, A .

TETRAHEDRON LETTERS, 1985, 26 (40) :4959-4960

[7] PALLADIUM-CATALYZED REDUCTIONS OF HALOAROMATIC AND NITROAROMATIC COMPOUNDS WITH TRIETHYLAMMONIUM FORMATE [J].

CORTESE, NA ;

HECK, RF .

JOURNAL OF ORGANIC CHEMISTRY, 1977, 42 (22) :3491-3494

[8] PALLADIUM-CATALYZED REDUCTIONS OF ALPHA, BETA-UNSATURATED CARBONYL-COMPOUNDS, CONJUGATED DIENES, AND ACETYLENES WITH TRIALKYLAMMONIUM FORMATES [J].

CORTESE, NA ;

HECK, RF .

JOURNAL OF ORGANIC CHEMISTRY, 1978, 43 (20) :3985-3987

[9]

COTTON FA, 1988, ADV INORG CHEM RAD, P77

[10] STEREOCONTROLLED SYNTHESIS OF STEROIDAL SIDE-CHAINS [J].

DAUBEN, WG ;

BROOKHART, T .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (01) :237-238

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