Kinetic and thermodynamic control of C(sp2)–H activation enables site-selective borylation

Jose B. Roque, Alex M. Shimozono, Tyler P. Pabst, Gabriele Hierlmeier, Paul O. Peterson, Paul J. Chirik

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

Catalysts that distinguish between electronically distinct carbon-hydrogen (C–H) bonds without relying on steric effects or directing groups are challenging to design. In this work, cobalt precatalysts supported by N-alkyl-imidazole–substituted pyridine dicarbene (ACNC) pincer ligands are described that enable undirected, remote borylation of fluoroaromatics and expansion of scope to include electron-rich arenes, pyridines, and tri- and difluoromethoxylated arenes, thereby addressing one of the major limitations of first-row transition metal C–H functionalization catalysts. Mechanistic studies established a kinetic preference for C–H bond activation at the meta-position despite cobalt-aryl complexes resulting from ortho C–H activation being thermodynamically preferred. Switchable site selectivity in C–H borylation as a function of the boron reagent was thereby preliminarily demonstrated using a single precatalyst.

Original languageEnglish (US)
Pages (from-to)1165-1171
Number of pages7
JournalScience
Volume382
Issue number6675
DOIs
StatePublished - Dec 1 2023

All Science Journal Classification (ASJC) codes

  • General

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