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General Access to <i>C</i>-Centered Radicals: Combining a Bioinspired Photocatalyst with Boronic Acids in Aqueous Media

Maheshwerreddy Chilamari, Jacob R. Immel, Steven Bloom

2020ACS Catalysis81 citationsDOI

Abstract

Carbon-centered radicals are indispensable building blocks for modern synthetic chemistry. In recent years, visible light photoredox catalysis has become a promising avenue to access C-centered radicals from a broad array of latent functional groups, including boronic acids. Herein, we present an aqueous protocol wherein water features a starring role to help transform aliphatic, aromatic, and heteroaromatic boronic acids to C-centered radicals with a bioinspired flavin photocatalyst. These radicals are used to deliver a diverse pool of alkylated products, including three pharmaceutically relevant compounds, via open-shell conjugate addition to disparate Michael acceptors. The mechanism of the reaction is investigated by computational studies, deuterium labeling, radical-trapping experiments, and spectroscopic analysis.

Topics & Concepts

RadicalChemistryPhotoredox catalysisAqueous solutionCatalysisPhotochemistryCombinatorial chemistryPhotocatalysisBoronic acidOrganic chemistryRadical Photochemical ReactionsSulfur-Based Synthesis TechniquesCatalytic C–H Functionalization Methods