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. 2016 Feb 24;138(7):2174-7.
doi: 10.1021/jacs.6b00250. Epub 2016 Feb 9.

Practical Ni-Catalyzed Aryl-Alkyl Cross-Coupling of Secondary Redox-Active Esters

Josep Cornella  1 , Jacob T Edwards  1 , Tian Qin  1 , Shuhei Kawamura  1 , Jie Wang  1 , Chung-Mao Pan  1 , Ryan Gianatassio  1 , Michael Schmidt  2 , Martin D Eastgate  2 , Phil S Baran  1
Affiliations

Practical Ni-Catalyzed Aryl-Alkyl Cross-Coupling of Secondary Redox-Active Esters

Josep Cornella et al. J Am Chem Soc. .

Abstract

A new transformation is presented that enables chemists to couple simple alkyl carboxylic acids with aryl zinc reagents under Ni-catalysis. The success of this reaction hinges on the unique use of redox-active esters that allow one to employ such derivatives as alkyl halides surrogates. The chemistry exhibits broad substrate scope and features a high degree of practicality. The simple procedure and extremely inexpensive nature of both the substrates and pre-catalyst (NiCl2·6H2O, ca. $9.5/mol) bode well for the immediate widespread adoption of this method.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
(A) A brief historical perspective of Ni-catalyzed alkyl-aryl cross-coupling. (B) An attempted intercepted Barton decarboxylation leads to a new hypothesis. (C) Invention of a new Ni-catalyzed decarboxylative cross-coupling.
Figure 2
Figure 2
Nickel-catalyzed decarboxylative cross-coupling performed on gram scale.
Figure 3
Figure 3
(A) Working hypothesis for the “redox-active” ester cross-coupling with aryl zinc reagents. (B) A stoichiometric experiment in support of a radical intermediate. (C) Ring opening of a carboxylic acid bearing a cyclopropane moiety.
See this image and copyright information in PMC

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