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Date SM, Singh R, Ghosh SK. The unprecedented reaction of dimethylsulfonium methylide with Michael acceptors: synthesis of 1-substituted vinyl silanes and styrenes. Org Biomol Chem. 2005;3(18):3369-78doi: 10.1039/b509102k.
Date, S. M., Singh, R., & Ghosh, S. K. (2005). The unprecedented reaction of dimethylsulfonium methylide with Michael acceptors: synthesis of 1-substituted vinyl silanes and styrenes. Organic & biomolecular chemistry, 3(18), 3369-78. https://doi.org/10.1039/b509102k
Date, Sonali M, et al. "The unprecedented reaction of dimethylsulfonium methylide with Michael acceptors: synthesis of 1-substituted vinyl silanes and styrenes." Organic & biomolecular chemistry vol. 3,18 (2005): 3369-78. doi: https://doi.org/10.1039/b509102k
Date SM, Singh R, Ghosh SK. The unprecedented reaction of dimethylsulfonium methylide with Michael acceptors: synthesis of 1-substituted vinyl silanes and styrenes. Org Biomol Chem. 2005 Sep 21;3(18):3369-78. doi: 10.1039/b509102k. Epub 2005 Aug 15. PMID: 16132099.
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Org Biomol Chem. 2005 Sep 21;3(18):3369-78. doi: 10.1039/b509102k. Epub 2005 Aug 15.

The unprecedented reaction of dimethylsulfonium methylide with Michael acceptors: synthesis of 1-substituted vinyl silanes and styrenes.

Organic & biomolecular chemistry

Sonali M Date, Rekha Singh, Sunil K Ghosh

Affiliations

  1. Bio-Organic Division, Bhabha Atomic Research Centre, Trombay. Mumbai 400 085, India.

PMID: 16132099 DOI: 10.1039/b509102k

Abstract

Rather than the usual cyclopropanation, conditions for an unprecedented elimination reaction from the adduct of dimethylsulfonium methylide and various Michael acceptors have been established leading to functionalized 1-substituted alkenes. In silyl substituted substrates (2a and 2h), where a facile Peterson-type olefination is possible from the adduct; elimination took place instead to give functionalized 1-substituted vinyl silanes. Aryl substituted Michael acceptors (2b-e, 2g and 2i-k) also underwent a similar kind of olefination to give 1-substituted styrene derivatives with moderate yields along with a side product, which arose by nucleophilic demethylation from the adduct of dimethylsulfonium methylide and arylidene malonates. Hammett studies revealed that selectivity for olefination vs. demethylation increases as the aryl substituent becomes more electron deficient. Alkylidene malonates (2f and 2l) with a beta-alkyl substituent did not favour the olefination process. Sequential addition of Michael acceptors and alkyl halides to a mixture of dimethylsulfonium methylide and sodium dimsylate provided olefination followed by alkylation on the active methine group. A mechanistic pathway has been formulated from the studies of a few sulfonium methylides.

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