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. 2016 Jan 20;138(2):475-8.
doi: 10.1021/jacs.5b10963. Epub 2015 Dec 24.

Base-Free Photoredox/Nickel Dual-Catalytic Cross-Coupling of Ammonium Alkylsilicates

Matthieu Jouffroy  1 , David N Primer  1 , Gary A Molander  1
Affiliations

Base-Free Photoredox/Nickel Dual-Catalytic Cross-Coupling of Ammonium Alkylsilicates

Matthieu Jouffroy et al. J Am Chem Soc. .

Abstract

Single-electron transmetalation is recognized as an enabling technology for the mild transfer of alkyl groups to transition metal catalysts in cross-coupling reactions. Hypercoordinate silicates represent a new and improved class of radical precursors because of their low oxidation potentials and the innocuous byproducts generated upon oxidation. Herein, we report the cross-coupling of secondary and primary ammonium alkylsilicates with (hetero)aryl bromides in good to excellent yields. The base-free conditions have exceptional protic group tolerance on both partners, permitting the cross-coupling of unprotected primary and secondary amines.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Proposed catalytic cycle for photoredox/Ni dual-catalysis cross-coupling with organometallic nucleophiles.
Scheme 1
Scheme 1. Successive Photoredox/Ni Dual Cross-Couplings
See this image and copyright information in PMC

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