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Updated: Sep 7, 2025

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Chiral Counteranion-Directed Catalytic Asymmetric Methylene Migration Reaction of Ene-Aldimines
Norie Momiyama1,2, Chanantida Jongwohan1,2, Naoya Ohtsuka1,2
1Institute for Molecular Science, Okazaki, Aichi 444-8787, Japan.
Abstract:
A catalytic asymmetric methylene migration reaction of ene-aldimines directed by chiral counteranions is developed, with the optimal catalyst identified as phenanthryl-substituted (R)-BINOL phosphate. Control experiments and density functional theory computations reveal the importance of the 2-hydroxy group of the ene-aldimine and attractive (e.g., OH···O, CH···O, CH···π, and π···π) interactions for high enantioselectivity (up to 74% ee). The results contribute to the design of asymmetric catalysis for the rearrangement of highly reactive iminium intermediates.
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