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. 2016 Oct 5;138(39):12715-12718.
doi: 10.1021/jacs.6b04789. Epub 2016 Sep 21.

Photochemical Nickel-Catalyzed C-H Arylation: Synthetic Scope and Mechanistic Investigations

Drew R Heitz  1 , John C Tellis  1 , Gary A Molander  1
Affiliations

Photochemical Nickel-Catalyzed C-H Arylation: Synthetic Scope and Mechanistic Investigations

Drew R Heitz et al. J Am Chem Soc. .

Abstract

An iridium photocatalyst and visible light facilitate a room temperature, nickel-catalyzed coupling of (hetero)aryl bromides with activated α-heterosubstituted or benzylic C(sp3)-H bonds. Mechanistic investigations on this unprecedented transformation have uncovered the possibility of an unexpected mechanism hypothesized to involve a Ni-Br homolysis event from an excited-state nickel complex. The resultant bromine radical is thought to abstract weak C(sp3)-H bonds to generate reactive alkyl radicals that can be engaged in Ni-catalyzed arylation. Evidence suggests that the iridium photocatalyst facilitates nickel excitation and bromine radical generation via triplet-triplet energy transfer.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Visible Light-Mediated C(sp3)–C(sp2) Cross-Coupling with Ni and Ir/Ru
Scheme 2
Scheme 2. THF/d8-THF Kinetic Isotope Effect Experiment
Scheme 3
Scheme 3. (A) Plausible Catalytic Cycle, (B) Pathway A: Intermolecular C–H Abstraction, and (C) Pathway B: Concerted Ni–Br Homolysis/C–H Abstraction
EnT = triplet–triplet energy transfer.
See this image and copyright information in PMC

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