Decarboxylative Borylation and Cross-Coupling of (Hetero)aryl Acids Enabled by Copper Charge Transfer Catalysis

• DOI: 10.1021/jacs.2c01630
• Publication Date: 2022-04-04T18:59:06Z
• Authors: Nathan W. Dow; P. Scott Pedersen; Tiffany Q. Chen; David C. Blakemore; Anne-Marie Decher...; Thomas Knauber; David W. C. MacMi...
• Keywords: Borylation

We report a copper-catalyzed strategy for arylboronic ester synthesis that exploits photoinduced ligand-to-metal charge transfer (LMCT) to convert (hetero)aryl acids into aryl radicals amenable ambient-temperature borylation. This near-UV process occurs under mild conditions, requires no prefunctionalization of the native acid, and operates broadly across diverse aryl, heteroaryl, pharmaceutical substrates. also one-pot procedure decarboxylative cross-coupling merges catalytic LMCT borylation palladium-catalyzed Suzuki-Miyaura arylation, vinylation, or alkylation with organobromides access range value-added products. The utility these protocols is highlighted through development heteroselective double-decarboxylative C(sp2)-C(sp2) coupling sequence, pairing halogenation processes two distinct (including substrates) subsequent cross-coupling.