Origin of the E/Z Selectivity in the Synthesis of Tetrasubstituted Olefins by Wittig Reaction of α-Fluorophosphonium Ylides: An Explanation for the Low Stereoselectivity Observed in Reactions of α-Alkoxy Aldehydes

Depré, Dominique;Vermeulen, Wim A. A.;Lang, Yolande;Dubois, Jean;Robiette, Raphaël;et.al.
(2017) Organic Letters — Vol. 19, n° 6, p. 1414-1417 (2017)

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  • Depré, Dominique
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  • Vermeulen, Wim A. A.
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  • Lang, Yolande
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  • Dubois, Jean
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  • Robiette, Raphaëlorcid-logoUCLouvain
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Abstract
A series of tetrasubstituted fluoroalkenes were synthesized in good yield and high E/Z selectivity (up to 96/4) by Wittig reaction between α-heterosubstituted ketones and α-fluorophosphonium ylides. A detailed study of factors that control stereoselectivity in these reactions shows that stereoselectivity is the result of stabilizing CH···F and N···C═O interactions in the addition TS leading to the E isomer. This analysis provides a rationale for the observed decrease in selectivity for reactions of stabilized ylides with α-alkoxy aldehydes.
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Depré, D., Vermeulen, W. A. A., Lang, Y., Dubois, J., Vandevivere, J., Vandermeersch, J., Huang, L., & Robiette, R. (2017). Origin of the E/Z Selectivity in the Synthesis of Tetrasubstituted Olefins by Wittig Reaction of α-Fluorophosphonium Ylides: An Explanation for the Low Stereoselectivity Observed in Reactions of α-Alkoxy Aldehydes. Organic Letters, 19(6), 1414-1417. https://doi.org/10.1021/acs.orglett.7b00344 (Original work published 2017)