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. 2012 Mar 16;14(6):1476-9.
doi: 10.1021/ol300217x. Epub 2012 Feb 23.

Synthesis of functionalized dialkyl ketones from carboxylic acid derivatives and alkyl halides

Alexander C Wotal  1 , Daniel J Weix
Affiliations

Synthesis of functionalized dialkyl ketones from carboxylic acid derivatives and alkyl halides

Alexander C Wotal et al. Org Lett. .

Abstract

Unsymmetrical dialkyl ketones can be directly prepared by the nickel-catalyzed reductive coupling of carboxylic acid chlorides or (2-pyridyl)thioesters with alkyl iodides or benzylic chlorides. A wide variety of functional groups are tolerated by this process, including common nitrogen protecting groups and C-B bonds. Even hindered ketones flanked by tertiary and secondary centers can be formed. The mechanism is proposed to involve the reaction of a (L)Ni(alkyl)(2) intermediate with the carboxylic acid derivative.

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Figures

Figure 1
Figure 1
The majority of methods couple a nucleophile and an electrophile, while this work couples two electrophiles.
Scheme 1
Scheme 1
Proposed Catalytic Cycle for Ketone Synthesis
See this image and copyright information in PMC

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