ENZYMATIC OXYGENATION OF SULFIDES WITH CYTOCHROME P-450 FROM RABBIT LIVER. STEREOCHEMISTRY OF SULFOXIDE FORMATION.

Article abstract of DOI:10.1246/bcsj.56.2300

Stereochemistry of enzymatic oxygenations of various diaryl, dialkyl and aryl alkyl sulfides to the corresponding sulfoxides with hepatic microsomes obtained from phenobarbital pretreated rabbit was investigated in comparison with those of nonenzymatic oxidations. Relative reactivity of the sulfides in the enzymatic oxygenation, based on the yields of the sulfoxides and the amount of oxygen absorption, depends upon the steric demand of the substituent in the oxygenation of 2-substituted thiochroman derivatives. A substantial asymmetric induction on the sulfur atom was always observed (e. g. , 54% e. e. for benzyl t-butyl sulfide). Formation of the sulfoxide with R-configuration predominated over that with S-configuration. The enzymatic oxygenation of all the unsymmetrical sulfides examined proceeded via the same steric course.