Alkylation of the alpha-carbanion of (R)-(-)-tert-butyl methyl sulfoxide (4) with n-propyl bromide afforded (+)-n-butyl tert-butyl sulfoxide (1) to which the absolute configuration (R) was ascribed. This assignment was confirmed by X-ray analysis of the complex 6 obtained from the enantiomerically pure sulfoxide (-)-1 and mercury chloride. Vibrational absorption and circular dichroism spectra of (+)-1 were measured in CDCl3 solution in the 2000-900 cm(-1) region and compared with the ab initio predictions of absorption and VCD spectra obtained with density functional theory using the B3LYP/6-31G basis set for different conformers of (R)-1. This comparison indicated also that (+)-1 is of the (R)-configuration.

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Comparison of the circular dichroism (CD) spectra of isomeric butyl ethyl sulfoxides, prepared from (-)-(S)-0-n-propyl ethanesulfinate and (-)-(S)-0-n-propyl tert-butanesulfinate with the appropriate organomagnesium reagents, as well as experiments on the synthesis of (-)-(R)-n-butyl tert-butyl sulfoxide strongly suggest retention of configuration in the reactions of either nonbranched alkanesulfinates with hindered organometallic reagents or sulfinates containing sterically demanding substituents at the sulfinyl sulfur atom with nonhindered organometallics.

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