In previous investigations the Michael-type reaction of 'soft' nucleophiles in the form of arene oxides with alkynyliodinium salts has been utilized to generate alkylidinecarbene intermediates which primarily undergo either a 1,5-intramolecular C-H insertion reaction to afford benzofurans or rearrangement to aryloxy alkynes.  In our investigations we have observed that while 1H-1-(1-alkynyl)-5-methyl-1,2,3-benziodoxathiole 3,3-dioxides bearing aryl groups follow this trend, those bearing aliphatic alkynyl groups display divergent reactivity.  The products of these reactions have been characterized as (2Z)-1,2-di(aryloxy)-2-alkenes in moderate yields.  This pathway has not been previously observed in reactions of phenoxides with alkynyl iodonium salts and mimics the reactions observed for the reaction of carboxylate anions with alkynyliodonium salts to afford a-acyloxyketones.

Synthesis of novel (2<i>Z</i>)-1,2-di(aryloxy)-2-alkenes from 1<i>H</i>-1-(1-alkynyl)-5-methyl-1,2,3-benziodoxathiole 3,3-dioxides

245th National Meeting (2013)

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Synthesis of novel (2Z)-1,2-di(aryloxy)-2-alkenes from 1H-1-(1-alkynyl)-5-methyl-1,2,3-benziodoxathiole 3,3-dioxides