<i>anti</i>‐Selective Borylstannylation of Alkynes with (<i>o</i>‐Phenylenediaminato)borylstannanes by a Radical Mechanism
Kensuke Suzuki, Naoki Sugihara, Yoshihiro Nishimoto, Makoto Yasuda
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.