钯催化甾体与有机锡烷的均相偶联反应。

Palladium-catalyzed homogeneous coupling reactions of steroids with organostannanes.

作者信息

Skoda-Földes R, Csákai Z, Kollár L, Horváth J, Tuba Z

机构信息

University of Veszprém, Department of Organic Chemistry, Veszprém, Hungary.

出版信息

Steroids. 1995 Dec;60(12):812-6. doi: 10.1016/0039-128x(95)00146-h.

DOI:10.1016/0039-128x(95)00146-h

PMID:8650704

Abstract

Direct and carbonylative coupling reactions of various steroid derivatives possessing iodo- and bromo-alkenyl moiety (17-iodo-androst-16-ene, 1, 17-bromoandrost-2,16-diene, 2, 17-iodo-4-aza-4-methylandrost-16-en-3-one, 3, 17-iodo-4-azaandrost-16-en-3-one, 4) with vinyltributylstannane and ethynyltributylstannane were carried out in the presence of various palladium catalysts. While carbonylation took place only with vinyltributylstannane, 17-vinyl-, and 17-ethynyl-delta 16 steroids were produced via direct coupling with vinyltributylstannane and ethynyltributylstannane, respectively. Activities of some catalysts based on Pd(0) and Pd(II) precursors were compared, and Pd(PPh3)4 was found to be superior to other complexes in most cases. In the coupling of 17-iodoandrost-16-ene with organostannanes Pd2(dba)3 + 8 AsPh3 in situ catalyst was found to be even more effective.

摘要

各种含有碘代和溴代烯基部分的甾体衍生物（17-碘代雄甾-16-烯，1；17-溴代雄甾-2,16-二烯，2；17-碘代-4-氮杂-4-甲基雄甾-16-烯-3-酮，3；17-碘代-4-氮杂雄甾-16-烯-3-酮，4）与乙烯基三丁基锡和乙炔基三丁基锡的直接偶联反应及羰基化偶联反应在各种钯催化剂存在下进行。虽然羰基化反应仅与乙烯基三丁基锡发生，但分别通过与乙烯基三丁基锡和乙炔基三丁基锡的直接偶联反应生成了17-乙烯基-δ16甾体和17-乙炔基-δ16甾体。比较了一些基于Pd(0)和Pd(II)前体的催化剂的活性，发现Pd(PPh3)4在大多数情况下优于其他配合物。在17-碘代雄甾-16-烯与有机锡的偶联反应中发现，原位催化剂Pd2(dba)3 + 8 AsPh3甚至更有效。