Selective Formal Carbene Insertion into Carbon‐Boron Bonds of Diboronates byN‐Trisylhydrazones

Abstract

AbstractBisborylalkanes play important roles in organic synthesis as versatile bifunctional reagents. The two boron moieties in these compounds can be selectively converted into other functional groups through cross‐coupling, oxidation or radical reactions. Thus, the development of efficient methods for synthesizing bisborylalkanes is highly demanded. Herein we report a new strategy to access bisborylalkanes through the reaction ofN‐trisylhydrazones with diboronate, in which the bis(boryl) methane is transformed into 1,2‐bis(boronates) via formal carbene insertion. Since theN‐trisylhydrazones can be readily derived from the corresponding aldehydes, this strategy represents a practical synthesis of 1,2‐diboronates with broad substrate scope. Mechanistic studies reveal an unusual neighboring group effect of 1,1‐bis(boronates), which accounts for the observed regioselectivity when unsymmetric 1,1‐diboronates are applied.