2-HALOVINYL ARYL SULFONES: NEW COUPLING REAGENTS FOR CARBOXAMIDE FORMATION¹

Synthesis and Reactions of 2-Chlorovinyl Sulfones

“…Two methods for the preparation of 2-chlorovinyl sulfones from the corresponding disulfides were presented in literature [12,17]. Thus, treatment of disulfide 7 with chlorine in CCl 4 at room temperature and then with ethyl acetate leads to formation of vinyl derivative 8.…”

“…Oxidation of compound with m-CPBA in CH 2 Cl 2 afforded E-isomer of chlorovinyl sulfone 9. Sulfuryl chloride as chlorinating agent of disulfides was also used in the synthesis of (E)-2chlorovinyl sulfones [17]. Some methods of synthesis of 2-chlorovinyl sulfones from different sulfones or sulfonyl chlorides were presented.…”

“…Interaction of 2-chlorovinyl sulfone 5 with MeOH, and then with BuLi / MeI afforded (E)-2-methoxy-1methyl-1-(phenylsulfonyl)ethylene (24) [30]. Addition of different carboxylic acid derivatives to 2-chlorovinyl sulfone 9 was investigated in details in article [17]. It is interesting, that addition of 4,4dimethyl-3-hydroxypentanoic acid to compound 9 afforded only carboxylic group addition product 25.…”

“…Addition of different N-nucleophiles (primary and secondary amines) to 2chlorovinyl sulfones readily proceeded in MeOH [31], EtOH [31,32], DMF [17], MeCN [33] and in the system Cs 2 CO 3 / 18-crown-6 / PhMe [34]. Interaction of 2-chlorovinyl sulfone 5 with hydroxylamine in the mixture EtOH / H 2 O afforded hydroxylamine 26.…”