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 - Funding Information:
The authors are grateful for financial support provided by the National Institute of General Medical Sciences (NIGMS), the NIH (under Award R35GM134897-03), the Princeton Catalysis Initiative, and kind gifts from Pfizer, Merck, Janssen, Bristol Myers Squibb, and Genentech. N.W.D. acknowledges Princeton University, E. C. Taylor and the Taylor family for an Edward C. Taylor Fellowship. P.S.P. thanks the NSF for a predoctoral fellowship (Award DGE-1656466). The content is solely the responsibility of the authors and does not necessarily represent the official views of NIGMS. The authors thank Rebecca Lambert for assistance in preparing this manuscript and Prof. Zhe Dong for helpful scientific discussions.
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.
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U2 - 10.1021/jacs.2c01630
DO - 10.1021/jacs.2c01630
M3 - Article
C2 - 35377627
AN - SCOPUS:85128209435
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 -