Donald D. Clarke and Shahrokh Saba. Fordham University, Bronx, NY
While enantiotopic hydrogens of a methylene group are isochronous in an achiral environment, this is no longer true in a chiral one. In an unrelated study of the diastereomers derived from the R and S enantiomers of 2- and 3-hexanol, we prepared the 1-(R)-10-camphorsulfonate ester of 1-hexanol. While all of the methylene hydrogens of 2- and 3-hexanol are diastereotopic due to the nearby asymmetric center, the methylene hydrogens at C-1 of 1-hexanol are enantiotopic; however, in the sulfonate ester they are diastereotopic and hence anisochronous with appreciably different chemical shifts. This signal shows 10 distinct lines. A simpler example of this phenomenon is provided by the ethyl ester of 1-(R)-10-camphorsulfonic acid (CSA). Instead of the usual quartet these protons now show 12 lines. This seems to be a useful pedagogic example to present to our students. Because of the difference in chemical shifts of the methylene hydrogens we can measure both the vicinal and the geminal coupling constants. Supported in part by a Faculty Research Grant from the Fordham University Research Council.