NHC-mediated photocatalytic para-selective C–H acylation of aryl alcohols: regioselectivity control via remote radical spiro cyclization

Friedel-Crafts reaction and transition-metal catalysis represent primary methodologies for arene acylation; however, suffer from certain limitations, such as electronic effect-dependent reactivity, regioselectivity issues, the necessity of directing group, and relatively exceptionally limited exploration in meta- and para-acylations. N-heterocyclic carbene (NHC) catalysis has recently emerged as a promising alternative strategy for arene acylation, offering distinct regioselectivity profiles that are challenging to achieve through known methods. Herein, an NHC-mediated photo-catalytic para-selective C–H acylation of aryl alcohols is disclosed. The reaction employs a remote radical-induced temporary spiro cyclization strategy, proceeding via tandem radical dearomatization, radical acylation, rearomatization processes. Combined experimental and computational mechanistic studies support the proposed reaction pathway and observe an exclusive para-selectivity regardless of the nature of the substituents on the substrates. Despite the less satisfactory yields, the current method exhibits non-electronic nature-based reactivity and regioselectivity, enabling quick access to acylated arenes that are difficult or impossible for reported methods.