Stereochemical aspects of the iodine(III)-mediated aziridination reaction of some cyclic allylic carbamates.
[reaction: see text] The iodine(III)-mediated aziridination reaction of an indolyl-substituted carbamate requires a Rh(II) catalyst and proceeds by a metallonitrene intermediate. Stepwise addition across the indole pi-bond followed by Rh(II) detachment generates a metal-free zwitterion, which ultimately leads to the observed products. In contrast, intramolecular aziridination of several cycloalkenyl carbamates does not require a Rh(II) catalyst and occurs via an iminoiodinane intermediate.
Padwa
Albert
A
Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA. chemap@emory.edu.
Stengel
Thomas
T
D000605:Amino Alcohols / Q000138:chemical synthesis; D001388:Aziridines / Q000737:chemistry; D002219:Carbamates / Q000138:chemical synthesis* / Q000737:chemistry; D003500:Cyclization; D007455:Iodine / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry; D013237:Stereoisomerism
D000605:Amino Alcohols; D001388:Aziridines; D002219:Carbamates; C033132:aziridine; D007455:Iodine; D012238:Rhodium