Palladium‐Catalyzed Desulfitative Mizoroki–Heck Couplings of Sulfonyl Chlorides with Mono‐ and Disubstituted Olefins: Rhodium‐Catalyzed Desulfitative Heck‐Type Reactions under Phosphine‐ and Base‐Free Conditions

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New conditions have been found for the desulfitative Mizoroki-Heck arylation and trifluoromethylation of mono- and disubustituted olefins with arenesulfonyl and trifluoromethanesulfonyl chlorides. Thus (E)-1,2-disubstituted alkenes with high stereoselectivity and 1,1,2-disubstituted alkenes with 12:1 to 21:1 E/Z steroselectivity can be obtained. Herrmann's palladacycle at 0.1 mol % is sufficient to catalyze these reactions, for which electron-rich or electron-poor sulfonyl chlorides and alkenes are suitable. If phosphine- and base-free conditions are required, 1 mol % [RhCl(C(2)H(4))(2)] catalyzes the desulfitative cross-coupling reactions. Contrary to results reported for [RuCl(2)(PPh(3))(2)]-catalyzed coupling reactions with sulfonyl chlorides, the palladium and rhodium desulfitative Mizoroki-Heck coupling reactions are not inhibited by radical scavenging agents. Possible sulfones arising from the sulfonylation of alkenes at 60 degrees C are not desulfitated at higher temperatures in the presence of the Pd or Rh catalysts.