| Autor: |
Dow NW; Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, United States., Pedersen PS; Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, United States., Chen TQ; Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, United States., Blakemore DC; Worldwide Research and Development, Pfizer, Inc., Eastern Point Road, Groton, Connecticut 06340, United States., Dechert-Schmitt AM; Worldwide Research and Development, Pfizer, Inc., Eastern Point Road, Groton, Connecticut 06340, United States., Knauber T; Worldwide Research and Development, Pfizer, Inc., Eastern Point Road, Groton, Connecticut 06340, United States., MacMillan DWC; Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, United States. |
| Abstrakt: |
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(sp 2 )-C(sp 2 ) coupling sequence, pairing copper-catalyzed LMCT borylation and halogenation processes of two distinct acids (including pharmaceutical substrates) with subsequent Suzuki-Miyaura cross-coupling. |
