源自官能化炔烃的氧杂硅杂环戊烯的形成与应用。

Formation and utility of oxasilacyclopentenes derived from functionalized alkynes.

作者信息

Clark Timothy B, Woerpel K A

机构信息

Department of Chemistry, University of California, Irvine, California 92697-2025, USA.

出版信息

J Am Chem Soc. 2004 Aug 11;126(31):9522-3. doi: 10.1021/ja047498f.

DOI:10.1021/ja047498f

PMID:15291539

Abstract

Oxasilacyclopentenes were shown to be synthetically useful masked allylic alcohols constructed in high yields and regioselectivities from terminal and internal alkynes. Several functional groups were shown to be tolerated utilizing silver-catalyzed silacyclopropenation of alkynes. In situ insertion of various carbonyl compounds into silacyclopropenes afforded regioselective formation of oxasilacyclopentenes. Elaboration of the oxasilacyclopentenes displayed the synthetic utility of these substrates. Both diastereoselective hydrogenation and Diels-Alder reactions utilizing the vinylsilane functionality demonstrated the reactivity and synthetic utility of oxasilacyclopentenes.

摘要

氧杂硅环戊烯被证明是合成中有用的掩蔽烯丙醇，可从端炔和内炔以高产率和区域选择性构建。利用银催化的炔烃硅环丙烷化反应，显示出几种官能团是可耐受的。各种羰基化合物原位插入硅环丙烯中，可区域选择性地形成氧杂硅环戊烯。对氧杂硅环戊烯的进一步衍生化展示了这些底物的合成效用。利用乙烯基硅烷官能团进行的非对映选择性氢化反应和狄尔斯-阿尔德反应都证明了氧杂硅环戊烯的反应活性和合成效用。