title: Intermolecular Aminocarbonylation of Alkenes using Concerted Cycloadditions of Iminoisocyanates.
abstract: The aminocarbonylation of alkenes is a powerful method for accessing the β-amino carbonyl motif that remains underdeveloped. Herein, the development of intermolecular aminocarbonylation reactivity of iminoisocyanates with alkenes is presented. This includes the discovery of a fluorenone-derived reagent, which was effective for many alkene classes and facilitated derivatization. Electron-rich substrates were most reactive, and this indicated that the LUMO of the iminoisocyanate is reacting with the HOMO of the alkene. Computational and experimental results support a concerted asynchronous [3 + 2] cycloaddition involving an iminoisocyanate, which was observed for the first time by FTIR under the reaction conditions. The products of this reaction are complex azomethine imines, which are precursors to valuable β-amino carbonyl compounds such as β-amino amides and esters, pyrazolones, and bicyclic pyrazolidinones. A kinetic resolution of the azomethine imines by enantioselective reduction (s = 13-43) allows access to enantioenriched products. Overall, this work provides a new tool to convert alkenes into β-amino carbonyl compounds.
authors.affiliation: Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Amanda
authors.initials: A
authors.lastname: Bongers
authors.affiliation: Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Christian
authors.initials: C
authors.lastname: Clavette
authors.affiliation: Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Wei
authors.initials: W
authors.lastname: Gan
authors.affiliation: Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Serge I
authors.initials: SI
authors.lastname: Gorelsky
authors.affiliation: Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Lyanne
authors.initials: L
authors.lastname: Betit
authors.affiliation: Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Kaitlyn
authors.initials: K
authors.lastname: Lavergne
authors.affiliation: Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Thomas
authors.initials: T
authors.lastname: Markiewicz
authors.affiliation: Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: Moon
authors.affiliation: Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Nicolas
authors.initials: N
authors.lastname: Das Neves
authors.affiliation: Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Nimrat K
authors.initials: NK
authors.lastname: Obhi
authors.affiliation: Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Amy B
authors.initials: AB
authors.lastname: Toderian
authors.affiliation: Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: André M
authors.identifier: 0000-0003-0667-6215
authors.initials: AM
authors.lastname: Beauchemin