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. 2015 Dec 4;17(23):5748-51.
doi: 10.1021/acs.orglett.5b02793. Epub 2015 Nov 20.

Palladium-Catalyzed α-Arylation of Aryl Nitromethanes

Kelsey F VanGelder  1 , Marisa C Kozlowski  1
Affiliations

Palladium-Catalyzed α-Arylation of Aryl Nitromethanes

Kelsey F VanGelder et al. Org Lett. .

Abstract

Catalytic conditions for the α-arylation of aryl nitromethanes have been discovered using parallel microscale experimentation, despite two prior reports of the lack of reactivity of these aryl nitromethane precursors. The method efficiently provides a variety of substituted, isolable diaryl nitromethanes. In addition, it is possible to sequentially append two different aryl groups to nitromethane. Mild oxidation conditions were identified to afford the corresponding benzophenones via the Nef reaction, and reduction conditions were optimized to afford several diaryl methylamines.

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Figures

Scheme 1
Scheme 1. Literature Precedent To Form Diaryl Nitromethanes
Scheme 2
Scheme 2. Exploration of Substrate Scope
Scheme 3
Scheme 3. Proposed Mechanism for the α-Arylation of Aryl Nitromethanes
Scheme 4
Scheme 4. Nef Reaction of Diaryl Nitromethanes To Afford Corresponding Benzophenones
Yields are for the two-step process from aryl nitromethane 1.
Scheme 5
Scheme 5. Reduction of Diaryl Nitromethanes to Diaryl Methylamines
Yields are for the two-step process from aryl nitromethane, 1.
Scheme 6
Scheme 6. One-Pot Diarylation of Nitromethane
See this image and copyright information in PMC

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