Exciton coupling in the CD spectra of chiral spiro-lambda 4-sulfanes and related sulfonium salts.

Abstract

Enantiomers of spiro-lambda 4-sulfanes 2-7 and related cyclic sulfonium salts 2c-7c have been obtained by stereospecific synthesis. Exciton splitting was observed in the CD spectra of spiro-lambda 4-sulfanes and sulfonium salts having both benzene and naphthalene-benzene rings. The absolute configurations were deduced from the sign of the couplet. Exciton couplets in the CD spectra of sulfonium salts and their parent lambda 4-sulfanes show the same sign which follows from the same orientation of the coupled electric transition moments due to their similar trigonal bipyramidal geometry. Based on the known stereomechanism of the formation of spiro-lambda 4-sulfanes and sulfonium salts as well as of their hydrolysis leading to the corresponding sulfoxides (2a-7a and 2b-7b), the absolute configurations of sulfoxides could also be deduced from the sign of exciton couplet in the CD spectra of related lambda 4-sulfanes and sulfonium salts.