Chemodivergent Sulfonylation of Enynones via Ionic and Radical Addition Modes of Sulfinic Acids

Different addition modes of sulfinic
acids were developed
for the
chemodivergent sulfonylation of enynones, where the ionic sulfonylation
to an alkyne moiety of enynones was effected through a salt-controlled syn-addition pathway. The radical sulfonylation of an alkene
moiety also provided the stereodefined sulfonylated alkenes. A one-pot
tandem sequence of the Ti(Oi-Pr)4-catalyzed
α-vinyl aldol condensation of (E)-β-chlorovinyl
ketones followed by the chemodivergent sulfonylations was also explored,
allowing for ready access to highly substituted dienes and enynes.