Temperature and solvent control of the stereoselectivity in the reactions of singlet oxygen with oxazolidinone-substituted enecarbamates.
Oxazolidinone-functionalized enecarbamates react stereoselectively with singlet oxygen to give methyldesoxybenzoin (MDB) in moderate to high enantiomeric excess. The stereochemical outcome depends on the E/Z substrate geometry, temperature, and solvent variables. The analysis of the differential activation parameters suggests a large contribution from the entropy term in determining the enantioselectivity. We demonstrate the utility of the temperature and solvent variables in determining the degree of the photochemical kinetic resolution of the enecarbamates; for example, in the photooxygenation at -70 degrees C in methanol, MDB may be obtained in methanol.
Joint Science Department, W.M. Keck Science Center, 925 North Mills Avenue, Claremont McKenna, Pitzer, and Scripps Colleges, Claremont, California 91711, USA.
Thomas
T
Poon
J
J
Sivaguru
Roberto
R
Franz
Steffen
S
Jockusch
Claudia
C
Martinez
Ilyas
I
Washington
Waldemar
W
Adam
Yoshihisa
Y
Inoue
Nicholas J
NJ
Turro
D001573:Benzoin / Q000031:analogs & derivatives* / Q000138:chemical synthesis; D002219:Carbamates / Q000737:chemistry*; D007700:Kinetics; D023303:Oxazolidinones / Q000737:chemistry*; D010777:Photochemistry; D026082:Singlet Oxygen / Q000737:chemistry*; D012997:Solvents; D013237:Stereoisomerism; D013696:Temperature; D013816:Thermodynamics
D002219:Carbamates; D023303:Oxazolidinones; D012997:Solvents; D026082:Singlet Oxygen; D001573:Benzoin