Radical hydroboration for the synthesis of organoboron compounds.

Abstract

Organoboron compounds demonstrate diverse applications in the fields of organic synthesis, materials science, and medicinal chemistry. Compared to the conventional hydroboration reaction, radical hydroboration serves as an alternative approach for the synthesis of organoborons via different mechanisms. In radical hydroboration, a boryl radical is initially generated from homolytic cleavage of a B-H or a B-B bond, which is then added to an unsaturated double bond to deliver a carbon radical. Subsequent hydrogen atom transfer or reduction of the carbon radical to form a carbanion followed by protonation gave the final product. Over the past few years, numerous efforts have been made for efficient synthesis of boryl radicals and the expansion of substrate scope of the radical hydroboration reaction. Here, we discuss the recent advancement of radical hydroboration and its associated mechanisms. Numerous radical hydroboration strategies employing N-heterocyclic carbene borane, bis(pinacolato)diboron and pinacolborane as the boron source were illustrated. Thermochemical, photochemical and electrochemical strategies for the generation of boryl radicals were also discussed in detail.