Chiroptical Properties of Sulfenamides

Article abstract of DOI:10.1021/jo01301a019

The ORD (and in some cases CD) spectra are presented for 11 sulfenamides of the structure R'SN(SO2Ar)CH(CH3)R (R'=CCl3, 4-chloro-2-methylphenyl, 2-nitrophenyl, 2,4-dinitrophenyl; R=phenyl, 1-naphthyl, benzyl; Ar=p-tolyl).A number of the spectra exhibit intense Cotton effects characteristic of inherently dissymmetric chromophores near 200 nm.The configuration at the asymmetric carbon atom seems to be related to the sign of the long-wavelength transition (near 350 nm) in the 2,4-dinitrobenzenesulfenamides.This is ascribed to an equilibrium asymmetric induction from the asymmetric center into the sulfenamide chiral axis whose configuration is reflected by the sign of this Cotton effect.It is suggested that examination of such derivatives may provide a useful method for determination of the absolute configuration of amines.