title: Formaldehyde as Tethering Organocatalyst: Highly Diastereoselective Hydroaminations of Allylic Amines.
abstract: Catalysts possessing sufficient activity to achieve intermolecular alkene hydroaminations under mild conditions are rare, and this likely accounts for the scarcity of asymmetric variants of this reaction. Herein, highly diastereoselective hydroaminations of allylic amines utilizing hydroxylamines as reagents and formaldehyde as catalyst are reported. This catalyst induces temporary intramolecularity, which results in high rate accelerations, and high diastereocontrol with either chiral allylic amines or chiral hydroxylamines. The reaction scope includes internal alkenes. Overall this work provides a new, stereocontrolled route to form complex vicinal diamines.
authors.affiliation: Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie-Curie, Ottawa, ON K1N 6N5, Canada.
authors.forename: Colin R
authors.initials: CR
authors.lastname: Hesp
authors.affiliation: Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie-Curie, Ottawa, ON K1N 6N5, Canada.
authors.forename: Melissa J
authors.initials: MJ
authors.lastname: MacDonald
authors.affiliation: Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie-Curie, Ottawa, ON K1N 6N5, Canada.
authors.forename: M Mehdi
authors.initials: MM
authors.lastname: Zahedi
authors.affiliation: Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie-Curie, Ottawa, ON K1N 6N5, Canada.
authors.forename: Didier A
authors.initials: DA
authors.lastname: Bilodeau
authors.affiliation: Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie-Curie, Ottawa, ON K1N 6N5, Canada.
authors.forename: Shu-Bin
authors.initials: SB
authors.lastname: Zhao
authors.affiliation: Boehringer Ingelheim (Canada) Ltd., 2100 Cunard Street, Laval, QC H7S 2G5, Canada.
authors.forename: Marc
authors.initials: M
authors.lastname: Pesant
authors.affiliation: Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie-Curie, Ottawa, ON K1N 6N5, Canada.
authors.forename: André M
authors.initials: AM
authors.lastname: Beauchemin