Highly selective synthesis of (E)-3-methyl-1-trialkylsilyl-3-en-1-ynes via trans-selective alkynylation catalyzed by Cl2Pd(DPEphos) and stereospecific methylation with methylzincs catalyzed by Pd(tBu3P)2

被引：78

作者：

Shi, JC ^{[1
]}

Zeng, XZ ^{[1
]}

Negishi, E ^{[1
]}

机构：

[1] Purdue Univ, Herbert C Brown Labs Chem, W Lafayette, IN 47907 USA

来源：

ORGANIC LETTERS | 2003年 / 5卷 / 11期

关键词：

D O I：

10.1021/ol030017x

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

trans-Selective (greater than or equal to 98%) monoalkynylation of 1,1-dibromo-1-alkenes and 1,1-dichloro-1-alkenes catalyzed by Cl2Pd(DPEphos) followed by stereospecific methylation with Me2Zn or MeZnX (X = CI or Br) catalyzed by Pd((Bu3P)-Bu-t)(2) provides an efficient and stereoselective ( greater than or equal to 98%) route to 5, convertible to a wide variety of enynes and conjugated dienes. In the cases of 1,1-dibromo-l-alkenes, the Sonogashira alkynylation may also be satisfactory, but it is distinctly less satisfactory than the alkynylzinc reaction in cases where 1,1-dichloro-1-alkenes are-used.

引用

页码：1825 / 1828

页数：4

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