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

TY - JOUR

T1 - Decarboxylative Borylation and Cross-Coupling of (Hetero)aryl Acids Enabled by Copper Charge Transfer Catalysis

AU - Dow, Nathan W.

AU - Pedersen, P. Scott

AU - Chen, Tiffany Q.

AU - Blakemore, David C.

AU - Dechert-Schmitt, Anne Marie

AU - Knauber, Thomas

AU - Macmillan, David W.C.

N1 - Publisher Copyright: © 2022 American Chemical Society. All rights reserved.

PY - 2022/4/13

Y1 - 2022/4/13

N2 - 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 to 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, and pharmaceutical substrates. We also report a one-pot procedure for decarboxylative cross-coupling that merges catalytic LMCT borylation and palladium-catalyzed Suzuki-Miyaura arylation, vinylation, or alkylation with organobromides to access a range of value-Added products. The utility of these protocols is highlighted through the development of a heteroselective double-decarboxylative C(sp2)-C(sp2) coupling sequence, pairing copper-catalyzed LMCT borylation and halogenation processes of two distinct acids (including pharmaceutical substrates) with subsequent Suzuki-Miyaura cross-coupling.

AB - 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 to 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, and pharmaceutical substrates. We also report a one-pot procedure for decarboxylative cross-coupling that merges catalytic LMCT borylation and palladium-catalyzed Suzuki-Miyaura arylation, vinylation, or alkylation with organobromides to access a range of value-Added products. The utility of these protocols is highlighted through the development of a heteroselective double-decarboxylative C(sp2)-C(sp2) coupling sequence, pairing copper-catalyzed LMCT borylation and halogenation processes of two distinct acids (including pharmaceutical substrates) with subsequent Suzuki-Miyaura cross-coupling.

UR - https://www.scopus.com/pages/publications/85128209435

UR - https://www.scopus.com/pages/publications/85128209435#tab=citedBy

U2 - 10.1021/jacs.2c01630

DO - 10.1021/jacs.2c01630

M3 - Article

C2 - 35377627

SN - 0002-7863

VL - 144

SP - 6163

EP - 6172

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 14

ER -