Stereoelectronic Effects in Cyclic Sulfoxides, Sulfones, and Sulfilimines: Application of the Perlin Effect to Conformational Analysis

Abstract

The 1JC--H coupling constants in conformationally constrained sulfoxides, bissulfoxides, sulfoxide-sulfones, and sulfilimines derived from 2-benzylidene-1,3-dithiane and 2-(2,2-dimethylpropylidene)-1,3-dithiolane were measured by means of HMQC and HSQC NMR experiments and the Perlin effects were calculated. The type and the relative configuration of S==X groups (X= O, NTos) in these compounds have a strong influence on the magnitude of coupling constants for axial and equatorial C--H bonds, respectively. Axial S==O bonds give rise to a stereoelectronic effect on antiperiplanar axial C--H bonds. The resultant weakening of the respective C--H bonds leads to a smaller coupling constant than for a respective equatorial C--H bond. Equatorial S==O groups have an influence on beta-C--H bonds through a homoanomeric effect. Here, the axial C--H bond is weakened and a smaller coupling constant is measured. Sulfilimine groups show similar effects to sulfoxide groups.