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

Nathan W. Dow, P. Scott Pedersen, Tiffany Q. Chen, David C. Blakemore, Anne Marie Dechert-Schmitt, Thomas Knauber, David W.C. Macmillan

Research output: Contribution to journalArticlepeer-review

Abstract

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.

Original languageEnglish (US)
Pages (from-to)6163-6172
Number of pages10
JournalJournal of the American Chemical Society
Volume144
Issue number14
DOIs
StatePublished - Apr 13 2022

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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