通过Cl2Pd(DPEphos)催化的反式选择性炔基化反应以及Pd(tBu3P)2催化的甲基锌立体定向甲基化反应，高度选择性合成(E)-3-甲基-1-三烷基甲硅烷基-3-烯-1-炔。
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.
作者信息
Shi Ji-Cheng, Zeng Xingzhong, Negishi Ei-Ichi
机构信息
Herbert C. Brown Laboratories of Chemistry, Purdue University, West Lafayette, Indiana 47907-2084, USA.
出版信息
Org Lett. 2003 May 29;5(11):1825-8. doi: 10.1021/ol030017x.
[reaction: see text] trans-Selective (>or=98%) monoalkynylation of 1,1-dibromo-1-alkenes and 1,1-dichloro-1-alkenes catalyzed by Cl(2)Pd(DPEphos) followed by stereospecific methylation with Me(2)Zn or MeZnX (X= Cl or Br) catalyzed by Pd((t)()Bu(3)P)(2) provides an efficient and stereoselective (>or=98%) route to 5, convertible to a wide variety of enynes and conjugated dienes. In the cases of 1,1-dibromo-1-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.
[反应：见正文] 由Cl(2)Pd(DPEphos)催化的1,1-二溴-1-烯烃和1,1-二氯-1-烯烃的反式选择性（≥98%）单炔基化反应，随后由Pd((t)()Bu(3)P)(2)催化用Me(2)Zn或MeZnX（X = Cl或Br）进行立体定向甲基化反应，提供了一条高效且立体选择性（≥98%）合成5的路线，5可转化为多种烯炔和共轭二烯。在1,1-二溴-1-烯烃的情况下，Sonogashira炔基化反应也可能令人满意，但在使用1,1-二氯-1-烯烃的情况下，它明显不如炔基锌反应令人满意。
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