Rhodium-Catalyzed Alkene Difunctionalization with Nitrenes.
The Rh(II) -catalyzed oxyamination and diamination of alkenes generate 1,2-amino alcohols and 1,2-diamines, respectively, in good to excellent yields and with complete regiocontrol. In the case of diamination, the intramolecular reaction provides an efficient method for the preparation of pyrrolidines, and the intermolecular reaction produces vicinal amines with orthogonal protecting groups. These alkene difunctionalizations proceed by aziridination followed by nucleophilic ring opening induced by an Rh-bound nitrene generated in situ, details of which were uncovered by both experimental and theoretical studies. In particular, DFT calculations show that the nitrogen atom of the putative [Rh]2 =NR metallanitrene intermediate is electrophilic and support an aziridine activation pathway by N⋅⋅⋅N=[Rh]2 bond formation, in addition to the N⋅⋅⋅[Rh]2 =NR coordination mode.
Institut de Chimie des Substances Naturelles, CNRS UPR 2301, Université Paris-Sud, Université Paris-Saclay, 1, av. de la Terrasse, 91198, Gif-sur-Yvette, France.
Jennifer
J
Ciesielski
Institut de Chimie des Substances Naturelles, CNRS UPR 2301, Université Paris-Sud, Université Paris-Saclay, 1, av. de la Terrasse, 91198, Gif-sur-Yvette, France.
Geoffroy
G
Dequirez
Institut de Chimie des Substances Naturelles, CNRS UPR 2301, Université Paris-Sud, Université Paris-Saclay, 1, av. de la Terrasse, 91198, Gif-sur-Yvette, France.
Pascal
P
Retailleau
Institut de Chimie des Substances Naturelles, CNRS UPR 2301, Université Paris-Sud, Université Paris-Saclay, 1, av. de la Terrasse, 91198, Gif-sur-Yvette, France. vincent.gandon@u-psud.fr.|Institut de Chimie Moléculaire et des Matériaux d'Orsay, CNRS UMR 8182, Université Paris-Sud, Université Paris-Saclay, bâtiment 420, 91405, Orsay CEDEX, France. vincent.gandon@u-psud.fr.
Vincent
http://orcid.org/0000-0003-1108-9410
V
Gandon
Institut de Chimie des Substances Naturelles, CNRS UPR 2301, Université Paris-Sud, Université Paris-Saclay, 1, av. de la Terrasse, 91198, Gif-sur-Yvette, France. philippe.dauban@cnrs.fr.
Philippe
http://orcid.org/0000-0002-1048-5529
P
Dauban
amination; oxyamination; reaction mechanisms; rhodium; synthetic methods