The relative efficiencies of the reaction of dibromides with biphenyl-2,2 -dithiol and 1,1 -binaphthalene-2,2 -dithiol to produce dithiacyclophanes have been examined as a potential route to chiral biaryl dithiols. Reaction of the resolvable dibromide 2,2 -bis(bromomethyl)-1,1 -binaphthalene with 1,1 -binaphthalene-2,2 -dithiol gave a diastereoisomeric mixture of dithiacyclophanes. Reaction of 1,1 -binaphthalene-2,2 -bis(methylenethiol) with 2,2 -bis(bromomethyl)-1,1 -binaphthalene gave a mixture including dinaphtho[2,1-c:1 ,2 -d]thiepin and the racemic diastereoisomer of 11,13,26,28-tetrahydrotetranaphtho[2,1-c:1 ,2 -e:2 ,1 -j:1 ,2 -l][1,8] dithiacyclotetradecin.