De novo synthesis of Troc-protected amines: intermolecular rhodium-catalyzed C-H amination with N-tosyloxycarbamates.
The rhodium-catalyzed intermolecular C-H insertion of the nitrene derived from 2,2,2-trichloroethyl-N-tosyloxycarbamate proceeded in good to excellent yields to produce a variety of Troc-protected amines. With cyclic aliphatic alkanes, it is possible to use only 2 equiv of substrate, whereas the reaction with aromatic alkanes is run neat. Not only does the nitrene insertion proceed in benzylic, secondary, and tertiary C-H bonds but also primary C-H insertion products were obtained in good yields. Finally, the use of chiral rhodium catalysts to provide an enantioselective version of this process is discussed. [reaction: see text].
Lebel
Hélène
H
Département de chimie, Université de Montréal, P.O. Box 6128, Station Downtown, Montréal, Québec, Canada, H3C 3J7. helene.lebel@umontreal.ca
Huard
Kim
K
D000473:Alkanes; D000586:Amination; D000588:Amines / Q000737:chemistry*; D002219:Carbamates / Q000138:chemical synthesis*; D002254:Carbonates / Q000737:chemistry; D002384:Catalysis; D011188:Potassium / Q000737:chemistry; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism; D014105:Tosyl Compounds / Q000138:chemical synthesis*
D000473:Alkanes; D000588:Amines; D002219:Carbamates; D002254:Carbonates; D014105:Tosyl Compounds; C037593:potassium carbonate; D012238:Rhodium; D011188:Potassium