Some ring-opening reactions of a diepoxide derived from (−)-quinic acid

A useful preparative route to nitrogen-containing, carbocyclic derivatives is described from (−)-quinic acid. (−)-Quinic acid was converted via the 3,4-O-cyclohexylidene-lactone into 1--3-O-tosyl-5-C-tosyloxymethylcyclohexane-1,2,5/3-tetrol (5) by sequential reduction with sodium borohydride, toluene-p-sulphonylation, and acid hydrolysis. Reaction of the disulphonate 5 with methanolic sodium methoxide afforded 1--1,2:5,7-dianhydro-5-C-hydroxymethylcyclohexane-1,2,3,5/0-tetrol (6). The ring-opening reactions of the diepoxide 6 with azide ion furnished a mixture of two diazides 9 and 13 in the ratio 4 to 1. The structure and conformation of the derived dibenzoates 10 and 14 have been determined by n.m.r. spectroscopy.