N-tosyloxycarbamates as a source of metal nitrenes: rhodium-catalyzed C-H insertion and aziridination reactions.
The rhodium-catalyzed decomposition of N-tosyloxycarbamates to generate metal nitrenes which undergo intramolecular C-H insertion or aziridination reaction is described. Aliphatic N-tosyloxycarbamates produce oxazolidinones with high yields and stereospecificity through insertion in benzylic, tertiary, and secondary C-H bonds. Intramolecular aziridination occurs with allylic N-tosyloxycarbamates to produce aziridines as single diastereomers. The reaction proceeds at room temperature using a rhodium catalyst and an excess of potassium carbonate and does not require the use of strong oxidant, such as hypervalent iodine reagents. A rhodium nitrene species is presumably involved, as both reactions are stereospecific.
Lebel
Hélène
H
Département de Chimie, Université de Montréal, C.P. 6128, Succursale Centre-ville, Montréal, Québec, Canada H3C 3J7. helene.lebel@umontreal.ca
Huard
Kim
K
Lectard
Sylvain
S
D001388:Aziridines / Q000138:chemical synthesis*; D002219:Carbamates / Q000737:chemistry*; D002384:Catalysis; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*
D001388:Aziridines; D002219:Carbamates; D009942:Organometallic Compounds; D012238:Rhodium