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- Title
Rhodium-Catalyzed Alkene Difunctionalization with Nitrenes.
- Authors
Ciesielski, Jennifer; Dequirez, Geoffroy; Retailleau, Pascal; Gandon, Vincent; Dauban, Philippe
- Abstract
The RhII-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.
- Subjects
NITRENES; PLATINUM group; RHODIUM; INTERMEDIATES (Chemistry); NITROGEN compounds
- Publication
Chemistry - A European Journal, 2016, Vol 22, Issue 27, p9338
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201600393