title: Asymmetric Brønsted Base Catalyzed and Directed [3+2] Cycloaddition of 2-Acyl Cycloheptatrienes with Azomethine Ylides.
abstract: Conjugated cyclic trienes have the potential for different types of cycloaddition reactions. In the present work, we will, in a novel asymmetric cycloaddition reaction, demonstrate that the organocatalytic reaction of 2-acyl cycloheptatrienes with azomethine ylides proceeds as a [3+2] cycloaddition, which is in contrast to the Lewis acid-catalyzed reaction, in which a [3+6] cycloaddition takes place. In the presence of a chiral organosuperbase, 2-acyl cycloheptatrienes react in a highly enantioselective manner in the [3+2] cycloaddition with azomethine ylides, providing the 1,3-dipolar cycloaddition product in high yields and up to 99 % ee. It is also shown that the diene formed by the reaction can undergo stereoselective dihydroxylation, bromination, and cycloaddition reactions. Finally, based on experimental observations, some mechanistic considerations are discussed.
authors.affiliation: Chemistry Department, Aarhus University, Langelandsgade 140, 8000, Aarhus C, Denmark.
authors.forename: Vibeke H
authors.initials: VH
authors.lastname: Lauridsen
authors.affiliation: Chemistry Department, Aarhus University, Langelandsgade 140, 8000, Aarhus C, Denmark.
authors.forename: Lise
authors.initials: L
authors.lastname: Ibsen
authors.affiliation: Chemistry Department, Aarhus University, Langelandsgade 140, 8000, Aarhus C, Denmark.
authors.forename: Jakob
authors.initials: J
authors.lastname: Blom
authors.affiliation: Chemistry Department, Aarhus University, Langelandsgade 140, 8000, Aarhus C, Denmark. kaj@chem.au.dk.
authors.forename: Karl Anker
authors.initials: KA
authors.lastname: Jørgensen
keywords: Synthetic methods; azomethine ylides; brønsted base catalysis; conjugated cyclic trienes; cycloaddition