A traceless arylsulfinate mediator strategy has been developed to switch the reaction course of β-chlorovinyl ketones with N-hydroxyamine. The soft α-vinyl enolization of (E)-β-chlorovinyl ketones was conducted in the presence of sodium arylsulfinate to give transient alkenyl sulfones that in turn reacted with NH 2 OH to give novel access to N-hydroxypyrroles. The mechanistic studies revealed the initial formation of oxazine intermediates that rearranged to thermodynamically stable aromatic products, N-hydroxypyrroles, under microwaveassisted heating conditions.

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) 4catalyzed 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.

Sodium sulfinate addition to (E)-β-chlorovinyl ketones followed by the aerobic cycloisomerization of alkenyl sulfone intermediates has been established for the synthesis of 3-sulfonyl furans. The optimal cycloisomerization catalyst system was identified to be Cu(OTf) 2 , where molecular oxygen acts as a terminal oxidant. With three points of structural variation in both β-chlorovinyl ketones and sodium sulfinates, the current aerobic cycloisomerization strategy allows the synthesis of highly functionalized and substituted furan derivatives.