无痕迹硅烷化β-C(sp)-H 键的醇通过全氟代缩醛。
Traceless Silylation of β-C(sp)-H Bonds of Alcohols via Perfluorinated Acetals.
机构信息
Department of Chemistry, University of California , Berkeley, California 94720, United States.
出版信息
J Am Chem Soc. 2018 Jan 31;140(4):1502-1507. doi: 10.1021/jacs.7b12150. Epub 2018 Jan 19.
Abstract
We report the silylation of primary C-H bonds located β to secondary and tertiary alcohols by exploiting perfluorinated esters as traceless directing groups. The conversion of a secondary or tertiary alcohol to a perfluoroalkyl ester and conversion of the ester to the corresponding silyl acetals by hydrosilylation allows for selective β-C(sp)-H silylation catalyzed by the combination of [Ir(cod)OMe] and MePhen (3,4,7,8-tetramethyl-1,10-phenanthroline) to form 6-membered dioxasilinane. Tamao-Fleming oxidation of these dioxasilinane leads to 1,2 diols. The developed sequence was applied to a series of natural products containing hydroxyl groups.
摘要
我们通过利用全氟酯作为无痕迹导向基团，实现了伯 C-H 键与β位仲醇和叔醇的硅烷化反应。通过硅氢化反应，仲醇或叔醇可以转化为全氟烷基酯，酯再转化为相应的硅基缩醛，然后在[Ir(cod)OMe]和 MePhen（3,4,7,8-四甲基-1,10-菲咯啉）的组合催化下，选择性地进行β-C(sp)-H 硅烷化反应，形成六元二氧硅杂环戊烷。这些二氧硅杂环戊烷的 Tamao-Fleming 氧化反应得到 1,2-二醇。所开发的序列被应用于一系列含有羟基的天然产物。
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