posted on 2021-09-07, 13:44authored byQiqiang Xie, Guangbin Dong
Boron-homologation
reactions represent an efficient and programmable
approach to prepare alkylboronates, which are valuable and versatile
synthetic intermediates. The typical boron-homologation reaction,
also known as the Matteson reaction, involves formal carbenoid insertions
into C–B bonds. Here we report the development of aza-Matteson
reactions via carbenoid insertions into the N–B bonds of aminoboranes.
By changing the leaving groups of the carbenoids and altering Lewis
acid activators, selective mono- and double-methylene insertions can
be realized to access various α- and β-boron-substituted
tertiary amines, respectively, from common secondary amines. The derivatization
of complex amine-containing bioactive molecules, diverse functionalization
of the boronate products, and sequential insertions of different carbenoids
have also been achieved.