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Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus
Published on: October 3, 2014
A Metallaphotoredox Strategy for the Cross-Electrophile Coupling of α-Chloro Carbonyls with Aryl Halides
Tiffany Q Chen1, David W C MacMillan1
1Merck Center for Catalysis at, Princeton University, Washington Road, Princeton, NJ, 08544, USA.
Abstract:
Here, we demonstrate that a metallaphotoredox-catalyzed cross-electrophile coupling mechanism provides a unified method for the α-arylation of diverse activated alkyl chlorides, including α-chloroketones, α-chloroesters, α-chloroamides, α-chlorocarboxylic acids, and benzylic chlorides. This strategy, which is effective for a wide variety of aryl bromide coupling partners, is predicated upon a halogen atom abstraction/nickel radical-capture mechanism that is generically successful across an extensive range of carbonyl substrates. The construction and use of arylacetic acid products have further enabled two-step protocols for the delivery of valuable building blocks for medicinal chemistry, such as aryldifluoromethyl and diarylmethane motifs.
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