Furan- and indole-derived boronate complexes react with alkyl iodides under radical (photoredox) or polar (SN 2) conditions to generate three-component alkylation products with high efficiency and complete stereospecificity. The methodology allows the incorporation of versatile functional groups such as nitriles, ketones, esters, sulfones, and amides, providing rapid access to complex chiral heteroaromatic molecules in enantioenriched form. Interestingly, while indolyl boronate complexes react directly with alkyl halides in a polar pathway, furyl boronates require photoredox catalysis. Careful mechanistic analysis revealed that the boronate complex not only serves as a substrate in the reaction but also acts as a reductive quencher for the excited state of the photocatalyst.
Keywords: alkylation; boron; heterocycles; metallate rearrangement; photoredox catalysis.
© 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.