An α-ester disulfide is shown to be a useful precursor for the preparation of several α-sulfone disulfides. These new α-sulfone disulfides are all fungitoxic against Aspergillus niger and Aspergillus flavus. RSO2CH2SSCH9
The first known examples of direct displacement of RSO2 groups from C(sp3) are described. The successful displacements are rationalized in terms of related experimental results and Coulombic stabilization in transition states, anticipated from modern MO computations on ground state structures.
Novel silica-induced controlled disproportionation of α-mercaptosulfones produces α-mercapto α′-sulfonyl sulfides. Its discovery and exploitation, as the heart of a new process – vault isomerization – permits the elaboration of a more efficient synthesis of a previously described synthetic precursor.