The pummerer and the thio‐claisen–type rearrangements of naphtho[1,8‐bc]‐1,5‐dithiocin monooxide and N‐p‐tosylsulfilimine

Abstract Naphtho[1,8‐bc]‐1,5‐dithiocin N‐p‐tosylsulfilimine ( 8 ) and monosulfoxide ( 9 ) were prepared. On treatment with conc. H 2 SO 4 , both the sulfilimine ( 8 ) and sulfoxide ( 9 ) gave the dithia dication which was converted to the sulfoxide by hydrolysis. The H–D exchange reaction of ( 8 ) took place highly regioselectively to afford the monodeuterated ( 8–D ) at the a‐position of the N‐tosyl group. The Pummerer rearrangement reaction of monooxide ( 9 ) with acetic anhydride gave the a‐acetoxy derivative by the dication ( 10b ), while a new thio‐Claisen rearrangement of sulfilimine ( 8 ) t‐BuOK in CH 2 Cl 2 gave 2‐allyl‐naphtho[1,8‐bc]‐1,5‐dithiole. © John Wiley & Sons, Inc.