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J Org Chem
; 87(14): 9399-9407, 2022 07 15.
Article
in English
| MEDLINE
| ID: mdl-35736506
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.