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Synthesis of enyne and aryl vinyl sulfoxides: functionalization via Pummerer rearrangement

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Abstract

An efficient methodology for the synthesis of aryl-substituted vinyl sulfoxides through direct substitution of aryl-substituted alkynyl grignard reagents on menthyl-p-toluenesulfinate followed by Suzuki–Miyaura cross-coupling reaction has been developed. It has also been described that the reaction of alkyl-substituted and cycloalkyl-substituted alkynyl grignard reagents with menthyl-p-toluenesulfinate led to two products, i.e., alkynyl sulfoxide derivatives, as a result of substitution, and enyne sulfoxide derivatives, which resulted from substitution followed by Michael type addition. It was possible to selectively synthesize the enyne sulfoxide derivatives by changing the concentration of the grignard reagent. These alkenyl sulfoxides were transformed into the corresponding \({\upalpha }\)-thio aldehydes in high yields via additive Pummerer rearrangement.

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Acknowledgments

The authors are grateful for the financial support provided by the FAPESP—São Paulo Research Foundation (Grant 2012/00424-2 and 2011/11499-0 for a fellowship to FBS—2013/20553-4), the CNPq—National Council for Scientific and Technological Development (308.320/2010-7 to HAS), and the FINEP (Grant 01.09.0278.04, DCP).

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Authors and Affiliations

  1. Departamento de Farmácia, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, São Paulo, SP, Brazil

    Frederico B. Souza, Luiz M. Z. Argomedo & Hélio A. Stefani

  2. Instituto de Química, Universidade de São Paulo, São Paulo, SP, Brazil

    Anwar Shamim

  3. Instituto Butantã, São Paulo, SP, Brazil

    Daniel C. Pimenta

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  1. Frederico B. Souza
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  2. Anwar Shamim
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  3. Luiz M. Z. Argomedo
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  5. Hélio A. Stefani
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Correspondence to Hélio A. Stefani.

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Souza, F.B., Shamim, A., Argomedo, L.M.Z. et al. Synthesis of enyne and aryl vinyl sulfoxides: functionalization via Pummerer rearrangement. Mol Divers 19, 773–785 (2015). https://doi.org/10.1007/s11030-015-9619-x

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