α-Borylalkyl radicals: their distinctive reactivity in modern organic synthesis

Abstract

Organoborons are extremely important for synthetic organic chemistry; they can serve as advanced intermediates for a variety of transformations. Such a well-known transformation involves the loss of the boron moiety, creating alkyl radicals. Although these originally developed protocols for alkyl radical generation remain in active use today, in recent years their α-boryl carbon-centred radicals have been joined by a new array of radical generation strategies that offer a unique reactivity to forge a wider diversity of organoborons that often operate under mild and benign conditions. Herein, we will highlight the stability and reactivity of α-borylalkyl radicals and their remarkably recent advances in order to further utilise them for C-C and C-heteroatom bond formation. Their use for this purpose has been reported over the last decade in an attempt to guide the synthetic community. Various transition-metal and metal-free methods for their generation are presented, and more advanced photoredox approaches are discussed, mainly for the period of 2009-2019.