三氟甲磺酸三甲硅酯促进的一锅法烯醇硅烷形成——酮与炔丙基羧酸盐的烷基化反应

One-Pot Enol Silane Formation-Alkylation of Ketones with Propargyl Carboxylates Promoted by Trimethylsilyl Trifluoromethanesulfonate.

作者信息

Downey C Wade, Confair Danielle N, Liu Yiqi, Heafner Elizabeth D

机构信息

Gottwald Center for the Sciences , University of Richmond , 28 Westhampton Way , Richmond , Virginia 23173 , United States.

出版信息

J Org Chem. 2018 Oct 19;83(20):12931-12938. doi: 10.1021/acs.joc.8b01997. Epub 2018 Oct 8.

DOI:10.1021/acs.joc.8b01997

PMID:30248260

Abstract

Ketones readily undergo conversion to enol silanes in the presence of a trialkylamine base and trimethylsilyl trifluoromethanesulfonate (TMSOTf) and add to propargyl cations to yield β-alkynyl ketones. The propargyl cations are generated in the same reaction flask through the TMSOTf-promoted ionization of propargyl acetates or propargyl propionates. A range of enol silane precursors and propargyl carboxylates reacts efficiently (20 examples, up to 99% yield). Cyclization of a representative product in the presence of TMSOTf provided 61% yield of the trisubstituted furan.

摘要

在三烷基胺碱和三甲基甲硅烷基三氟甲磺酸酯（TMSOTf）存在下，酮类化合物很容易转化为烯醇硅烷，并与炔丙基阳离子加成生成β-炔基酮。炔丙基阳离子通过TMSOTf促进的炔丙基乙酸酯或炔丙基丙酸酯的离子化在同一反应烧瓶中生成。一系列烯醇硅烷前体和炔丙基羧酸盐能高效反应（20个例子，产率高达99%）。代表性产物在TMSOTf存在下环化，得到三取代呋喃，产率为61%。