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

被引：82

作者：

Dow, Nathan W. ^{[1
]}

Pedersen, P. Scott ^{[1
]}

Chen, Tiffany Q. ^{[1
]}

Blakemore, David C. ^{[2
]}

Dechert-Schmitt, Anne-Marie ^{[2
]}

Knauber, Thomas ^{[2
]}

MacMillan, David W. C. ^{[1
]}

机构：

[1] Princeton Univ, Merck Ctr Catalysis, Princeton, NJ 08544 USA

[2] Pfizer Inc, Worldwide Res & Dev, Groton, CT 06340 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2022年 / 144卷 / 14期

关键词：

KINETIC CHARACTERISTICS; ORGANOBORON CHEMISTRY; PHOTOREDOX CATALYSIS; CONJUGATE ADDITION; AROYLOXYL RADICALS; BOND FORMATION; COMPLEXES; REAGENTS; CHLORIDE; BIARYLS;

D O I：

10.1021/jacs.2c01630

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We report a copper-catalyzed strategy for arylboronic ester synthesis that exploits photoinduced ligand-to-metalcharge transfer (LMCT) to convert (hetero)aryl acids into aryl radicals amenable to ambient-temperature borylation. This near-UVprocess 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 mergescatalytic LMCT borylation and palladium-catalyzed Suzuki-Miyaura arylation, vinylation, or alkylation with organobromides toaccess a range of value-added products. The utility of these protocols is highlighted through the development of a heteroselectivedouble-decarboxylative C(sp2)-C(sp2) coupling sequence, pairing copper-catalyzed LMCT borylation and halogenation processesof two distinct acids (including pharmaceutical substrates) with subsequent Suzuki-Miyaura cross-coupling.

引用

页码：6163 / 6172

页数：10

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