甲磺酰氧基迁移作为各种官能化烯烃的立体选择性制备方法及其反应机理。

Mesyloxy-group migration as the stereoselective preparation method of various functionalized olefins and its reaction mechanism.

作者信息

Yamazaki T, Hiraoka S, Sakamoto J, Kitazume T

机构信息

Department of Bioengineering, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226-8501, Japan.

出版信息

Org Lett. 2001 Mar 8;3(5):743-6. doi: 10.1021/ol007060u.

DOI:10.1021/ol007060u

PMID:11259051

Abstract

[structure: see text]. It was demonstrated that mesylation of appropriate gamma,gamma-difluorinated allylic alcohols under usual conditions furnished the corresponding alpha,alpha-difluorinated allylic mesylates, possibly by way of 1,3-mesyloxy-group migration after formation of the expected "normal" intermediates, gamma,gamma-difluorinated allylic mesylates. This rearrangement was conveniently applied to the construction of trisubstituted allylic alcohols, alpha,beta-unsaturated esters, amides, or ketones in good to excellent chemical yields with exclusive E selectivities.

摘要

[结构：见正文]。结果表明，在通常条件下，适当的γ，γ-二氟烯丙醇进行甲磺酰化反应可得到相应的α，α-二氟烯丙基甲磺酸酯，可能是在形成预期的“正常”中间体γ，γ-二氟烯丙基甲磺酸酯后通过1,3-甲磺氧基迁移的方式。这种重排反应可方便地用于构建三取代烯丙醇、α，β-不饱和酯、酰胺或酮，化学产率良好至优异，且具有专一的E选择性。