Origin of the Stereoselectivity in (Ethoxycarbonyl)-, Cyano-, and Phenyl-Substituted (Arylsulfinyl)methyl Radicals

Article abstract of DOI:10.1002/hlca.19980810518

An explanation for the very high diastereoselectivity observed for the reactions of carbonyl-substituted (arylsulfmyl)methyl radicals is presented, based on experimental results and semiempirical calculations. The influence of dipole-dipole interactions, allylic 1,3-strain(A^1,3 strain), allylic 1,2-strain (A^1,3 strain), and coulombic interactions is discussed based on stereoselectivities observed with (alkoxycarbonyl)-, cyano-, and aryl-substituted (arylsulfinyl)methyl radicals. In the second part, the effect of solvents and Lewis acids on the stereoselectivity of. reactions of (arylsulfmyl)- and (alkylsulfinyl)benzyl radicals has been examined.