title: Substituent effects in Ugi-smiles reactions.
abstract: In a recent communication, we described the mechanism of the well-known Ugi-type reactions with a model system (J. Org. Chem. 2012, 77, 1361-1366). Herein, focusing on the Ugi-Smiles coupling, we study the effects of each of the four reactants on the energy profile to further explain the experimental results. The variations observed with different carbonyl compounds rely on their influence on the formation of the aryl-imidate, whereas the variations on the amine preferentially affect the Smiles rearrangement. The effect of substituents on the phenol derivative is seen upon both aryl-imidate formation and the rearrangement. The effect of the isocyanide substituents is less pronounced.
authors.affiliation: Ecole Normale Supérieure de Lyon, Laboratoire de Chimie, Université de Lyon, UMR 5182, 46 allée d'Italie, F-69364 Lyon Cedex 07, France.
authors.forename: Nicolas
authors.initials: N
authors.lastname: Chéron
authors.forename: Romain
authors.initials: R
authors.lastname: Ramozzi
authors.forename: Laurent
authors.initials: L
authors.lastname: El Kaïm
authors.forename: Laurence
authors.initials: L
authors.lastname: Grimaud
authors.forename: Paul
authors.initials: P
authors.lastname: Fleurat-Lessard