Racemic 1-(1′-isoquinolinyl)-2-naphthalenemethanol rac- 12 was prepared through a ligand coupling reaction of racemic 1-( tert-butylsulfinyl)isoquinoline rac- 7 with the 1-naphthyl Grignard reagent 10 . Resolution of rac- 12 was achieved through chromatographic separation of the Noe-lactol derivatives 14 and 15 , providing ( R)-(−)- 12 of >99% ee and ( S)-(+)- 12 of 90% ee. The ligand coupling reaction of optically enriched sulfoxide ( S)-(−)- 7 (62% ee) with Grignard reagent 10 furnished rac- 12 , with the absence of stereoinduction resulting from competing rapid racemisation of the sulfoxide 7 . Reaction of optically enriched ( S)-(−)- 7 with 2-methoxy-1-naphthylmagnesium bromide was also accompanied by racemisation of the sulfoxide 7 , and furnished optically active (+)-1-(2′-methoxy-1′-naphthyl)isoquinoline (+)- 3b in low enantiomeric purity (14% ee). The absolute configuration of (+)- 3b was assigned as R using circular dichroism spectroscopy, correcting an earlier assignment based on the Bijvoet method, but in the absence of heavy atoms. Optically active 2-pyridyl sulfoxides were found not to undergo racemisation analogous to the 1-isoquinolinyl sulfoxide 7 , with the ligand coupling reactions of ( R)-(+)- and ( S)-(−)-2-[(4′-methylphenyl)sulfinyl]-3-methylpyridines, ( R)-(+)- 17 and ( S)-(−)- 17 , with 2-methoxy-1-naphthylmagnesium bromide providing (−)- and (+)-2-(2′-methoxy-1′-naphthyl)-3-methylpyridines, (−)- 18 and (+)- 18 , in 53 and 60% ee, respectively. The free energy barriers to internal rotation in 3b and 18 have been determined, and the isoquinoline ( R)-(−)- 12 examined as a ligand in the enantioselectively catalysed addition of diethylzinc to benzaldehyde; ( R)-(−)- 12 was also converted to ( R)-(−)- N, N-dimethyl-1-(1′-isoquinolinyl)-2-naphthalenemethanamine ( R)-(−)- 19 , and this examined as a ligand in the enantioselective Pd-catalysed allylic substitution of 1,3-diphenylprop-2-enyl acetate with dimethyl malonate.