A novel free-radical ring contraction of a cyclic carbamate.
During a study on iodocyclocarbamation reactions of 2-styryl-4-piperidones, a novel ring contraction was observed. Iodocyclocarbamation of 2-styryl-4-piperidone 3 gave the bicyclic carbamate 4. Reduction of 4 under free-radical conditions effected a stereoselective ring contraction to provide oxazolidinone 6. A three-electron-three-center mechanism is proposed.
Williams
Alfred L
AL
Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204, USA.
Grillo
Teresa Abad
TA
Comins
Daniel L
DL
D001372:Aza Compounds / Q000138:chemical synthesis / Q000737:chemistry; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis / Q000737:chemistry; D002219:Carbamates / Q000737:chemistry*; D002384:Catalysis; D002845:Chromatography; D003500:Cyclization; D005609:Free Radicals; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D010881:Piperidones / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism
C456613:1-aza-5-iodo-3-oxa-4-phenylbicyclo(4.4.0)decane-2,8-dione; C456612:1-benzyloxycarbonyl-2-(2'-phenylethenyl)-4-piperidone; D001372:Aza Compounds; D001643:Bridged Bicyclo Compounds; D002219:Carbamates; D005609:Free Radicals; D010881:Piperidones