Conformational Assignment, Absolute Configuration, and Chiral Separation of All the Stereoisomers Created by the Combined Presence of Stereogenic Centers and Stereogenic Conformational Axes in a Highly Hindered 1,5-Naphthyl Sulfoxide

The presence of two stereogenic centers and of two stereogenic conformational axes in 2,6-dimethyl-1,5-bis(2-methyl-2-propylsulfinyl)naphthalene (1) entails the existence of 10 stereoisomers. In particular, both the meso form (1a) and the racemic form (1b) are constituted by three atropisomers; in the case of the latter (1b) each of them entails a pair of enantiomers (total of six species), whereas owing to the symmetry only one of the three atropisomers of the meso form (1a) yields a pair of enantiomers (a total of four species). Despite the low conformational interconversion barrier (18.5 kcal/mol) all of them have been separated by low temperature (-45°C) chiral HPLC. Their configurational and conformational assignment has been achieved by a combined use of NMR (both in solution and solid state) and on-line CD-detected chiral HPLC. The single crystal X-ray diffraction yielded the absolute configuration of one of the stereoisomers ((ZR,ER)-1b) from which all the others could be obtained by CD relationship.