title: Stereoselective and Versatile Preparation of Tri- and Tetrasubstituted Allylic Amine Scaffolds under Mild Conditions.
abstract: Significant progress has been observed in recent years in the synthesis of allylic amines, which are important building blocks in synthetic chemistry. Most of these processes are effective toward the preparation of allylic amines, with limited potential to introduce three or four different substituents on the olefinic unit in a stereocontrolled fashion. Therefore, the discovery of a mild and operationally simple protocol allowing such challenging stereoselective synthesis of multisubstituted allylic amines remains an inspiring target. Herein, we report the first general and practical methodology for the stereoselective synthesis of tri- and tetrasubstituted allylic amines based on Pd-catalyzed conversion of allyl surrogates readily obtained from cyclic vinyl carbonates. These rare conversions are characterized by excellent stereoselectivity, operational simplicity, mild reaction conditions, and wide scope in reaction partners. DFT studies were performed to rationalize the stereocontrol in these allylic amine formation reactions, and evidence is provided that the formation of a six-membered palladacyclic intermediate leads toward the formation of (Z)-configured allylic amine products.
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology , Av. Països Catalans 16, 43007 Tarragona, Spain.
authors.forename: Wusheng
authors.initials: W
authors.lastname: Guo
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology , Av. Països Catalans 16, 43007 Tarragona, Spain.
authors.forename: Luis
authors.initials: L
authors.lastname: Martínez-Rodríguez
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology , Av. Països Catalans 16, 43007 Tarragona, Spain.
authors.forename: Rositha
authors.initials: R
authors.lastname: Kuniyil
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology , Av. Països Catalans 16, 43007 Tarragona, Spain.
authors.forename: Eddy
authors.initials: E
authors.lastname: Martin
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology , Av. Països Catalans 16, 43007 Tarragona, Spain.
authors.forename: Eduardo C
authors.initials: EC
authors.lastname: Escudero-Adán
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology , Av. Països Catalans 16, 43007 Tarragona, Spain.|Departament de Química, Universitat Autònoma de Barcelona , 08193 Bellaterra, Catalonia, Spain.
authors.forename: Feliu
authors.initials: F
authors.lastname: Maseras
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology , Av. Països Catalans 16, 43007 Tarragona, Spain.|Catalan Institute of Research and Advanced Studies (ICREA) , Pg. Lluís Companys 23, 08010 Barcelona, Spain.
authors.forename: Arjan W
authors.initials: AW
authors.lastname: Kleij