anti-Selective Borylstannylation of Alkynes with (o-Phenylenediaminato)borylstannanes by a Radical Mechanism

Kensuke Suzuki; Naoki Sugihara; Yoshihiro Nishimoto; Makoto Yasuda

doi:10.1002/anie.202201883

anti-Selective Borylstannylation of Alkynes with (o-Phenylenediaminato)borylstannanes by a Radical Mechanism

Angew Chem Int Ed Engl. 2022 Jul 4;61(27):e202201883. doi: 10.1002/anie.202201883. Epub 2022 May 11.

Authors

Kensuke Suzuki¹, Naoki Sugihara¹, Yoshihiro Nishimoto^{1

2}, Makoto Yasuda^{1

2}

Affiliations

¹ Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka, 565-0871, Japan.
² Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, 2-1 Yamadaoka, Suita, Osaka, 565-0871, Japan.

PMID: 35485137
DOI: 10.1002/anie.202201883

Abstract

We have achieved the first anti-borylstannylation of alkynes by using (o-phenylenediaminato)borylstannanes. This reaction afforded 1-boryl-2-stannylalkenes with excellent regio- and stereoselectivity by a radical mechanism. This anti-addition manner is in sharp contrast to the syn-selectivity obtained during transition metal-catalyzed borylstannylation. The mild radical conditions enabled a broad substrate scope, and various types of aromatic and aliphatic alkynes were applicable. The origin of regio- and stereoselectivity was elucidated by DFT calculation of the reaction mechanism. The application of the borylstannylation products to cross- or homocoupling reactions provided ready access to either triarylethenes or bisborylbutadienes.

Keywords: Alkynes; Boron; Borylstannylation; Radical Reactions; Tin.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Alkynes*
Catalysis
Transition Elements*

Substances

Alkynes
Transition Elements