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Article Dans Une Revue Chemistry - A European Journal Année : 2017

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

Résumé

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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Chimie
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Dates et versions

hal-02046278 , version 1 (22-02-2019)

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Citer

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