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Published on: April 24, 2014
Accounting for Diradical Character through DFT. The Case of Vinyl Allene Oxide Rearrangement
Roberto Villar López1, Olalla Nieto Faza1, Carlos Silva López1
1Departamento de Química Orgánica, Campus Lagoas-Marcosende , 36310 Vigo, Spain.
Abstract:
The transformation of vinyl allene oxides into cyclopentenones is key to the biosynthesis of a number of hormone-like molecules in plants. Two competitive paths are generally accepted for this transformation: a concerted SN2-like mechanism and a stepwise path with a diradical oxyallyl intermediate. Recently, a new stepwise closed-shell path has been proposed that circumvents the key oxyallyl intermediate. In this work, we conduct a thorough computational investigation, including dynamic effects, to identify the most likely mechanism for this transformation.
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