NUCLEOPHILIC SUBSTITUTION AT TETRACOORINATE HEXAVALENT SULFUR . REACTION OF (-)-MENTHYL PHENYLMETHANESULFONATE WITH P-TOLYLMAGNESIUM BROMIDE

Menthyl phenylmethanesulfinate of configuration R at sulfur was stereospecifically oxidized to menthyl phenylmethanesulfonate with 90.2% 18O potassium permanganate. Treatment of this sulfonate ester with p-tolylmagnesium bromide gave (–)-benzyl p-tolylsulfone- 160, 18O, presumably of configuration S. Since the levorotatory sulfone had been prepared by oxidation of (R)-benzyl p-tolylsulfoxide, the reaction of the sulfonate ester with the Grignard reagent proceeded with inversion of configuration at sulfur. This constitutes the first example in which the stereochemistry of nucleophilic substitution at tetracoordinate hexavalent sulfur has been established. © 1969, American Chemical Society. All rights reserved.