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Vinyl (Thio)Ethers versus Enamines: A DFT Insight into Their Divergent Reactivities toward Nitroalkenes

Abstract : Despite their apparent similarities, vinyl (thio)ethers and enamines display divergent reactivities toward nitroalkenes. Whereas [4+2] cycloadduct derivatives are generally obtained in the first case, a variety of adducts are observed in the second, and depend on the substrates and reaction conditions. Herein, a rationalization of this versatility is proposed through a theoretical study, in which the interactions between these electron‐rich alkenes and nitroethylene are compared in conjugate addition, [4+2] and [2+2] cycloadditions, and ene reaction processes. The conjugate zwitterionic adduct is shown to play a key role. With vinyl (thio)ethers, its formation is disfavored, whereas, for enamines, it appears as a stabilized intermediate, leading to the thermodynamically favored formal ene adduct. This adduct is, however, kinetically disfavored, which opens up the way to control the selectivity of the whole process.
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https://hal-normandie-univ.archives-ouvertes.fr/hal-02046278
Contributor : Madeleine Roux-Merlin <>
Submitted on : Friday, February 22, 2019 - 3:39:47 PM
Last modification on : Thursday, July 30, 2020 - 3:08:48 AM

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H. Gérard, Isabelle Chataigner. Vinyl (Thio)Ethers versus Enamines: A DFT Insight into Their Divergent Reactivities toward Nitroalkenes. Chemistry - A European Journal, Wiley-VCH Verlag, 2017, 23 (55), pp.13711-13717. ⟨10.1002/chem.201701961⟩. ⟨hal-02046278⟩

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