Fluoride Ion-Initiated Decarboxylation of Silyl Alkynoates to Alkynylsilanes

Takahiro Kawatsu; Sho Kataoka; Norihisa Fukaya; Jun-Chul Choi; Kazuhiko Sato; Kazuhiro Matsumoto

doi:10.1021/acsomega.1c01256

Fluoride Ion-Initiated Decarboxylation of Silyl Alkynoates to Alkynylsilanes

ACS Omega. 2021 May 3;6(19):12853-12857. doi: 10.1021/acsomega.1c01256. eCollection 2021 May 18.

Authors

Takahiro Kawatsu¹, Sho Kataoka², Norihisa Fukaya¹, Jun-Chul Choi¹, Kazuhiko Sato¹, Kazuhiro Matsumoto¹

Affiliations

¹ Interdisciplinary Research Center for Catalytic Chemistry (IRC3), National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5, 1-1-1 Higashi, Tsukuba 305-8565, Ibaraki, Japan.
² Research Institute for Chemical Process Technology, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5, 1-1-1 Higashi, Tsukuba 305-8565, Ibaraki, Japan.

Abstract

This communication describes the development of a metal-free catalytic decarboxylation of silyl alkynoates to alkynylsilanes. Treatment of a silyl alkynoate with a catalytic amount of tetrabutylammonium difluorotriphenylsilicate (TBAT) in N,N-dimethylformamide at 150 °C resulted in decarboxylation to give the corresponding alkynylsilane in good to excellent yield (75 → 95%). The TBAT system was applicable to the decarboxylation of sterically demanding silyl alkynoates such as tert-butyldiphenylsilyl 3-phenylpropiolate. Mechanistic studies revealed that the tetrabutylammonium alkynoate derived from TBAT and the silyl alkynoate act as a catalyst for the decarboxylation.