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  4. Hidden intermediate activation: a concept to elucidate the reaction mechanism of the Schmittel cyclization of enyne–allenes
 
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Hidden intermediate activation: a concept to elucidate the reaction mechanism of the Schmittel cyclization of enyne–allenes
Dra. Durán-Guajardo, Rocío 
Barrales-Martínez, César
Matute, Ricardo A
10.1039/D2CP04684A
Royal Society of Chemistry
2023
The mechanistic paradigm in which the Schmittel cyclization transitions from one-step to stepwise has been investigated through the stabilization of a full hidden intermediate in the framework of the Diabatic Model of Intermediate Stabilization. Hidden intermediate activation was studied in silico employing quasi-classical trajectories and the Electron Localization Function. The stabilization of hidden intermediates achieved by substituting enyne–allenes with cyano and nitro groups generates the appearance of a partially hidden and an explicit intermediate, leading to one-step asynchronous biradical and stepwise biradical/zwitterionic mechanisms, respectively. The mechanistic feature associated with the activation level of the hidden intermediate arises from the Thornton effect and non-RRKM dynamics, where in the case of the CN-substituted system, despite having a single transition state, 54% of the effective trajectories remain in the intermediate zone after 540 fs, indicating that a mixture of mechanisms is observed.
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