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Reactions of HDDA-Derived Benzynes with Sulfides: Mechanism, Modes, and Three-Component Reactions
Junhua Chen1, Vignesh Palani1, Thomas R Hoye1
1Department of Chemistry, University of Minnesota , 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
Abstract:
We report here reactions of alkyl sulfides with benzynes thermally generated by the hexadehydro-Diels-Alder (HDDA) cycloisomerization. The initially produced 1,3-betaine (o-sulfonium/aryl carbanion) undergoes intramolecular proton transfer to generate a more stable S-aryl sulfur ylide. This can react in various manners, including engaging weak acids (HA) in the reaction medium. This can produce transient ion pairs ArSR2(+)A(-) that proceed to the products ArSR + RA. When cyclic sulfides are used, A(-) opens the ring and is incorporated into the product, an outcome that constitutes a versatile, three-component coupling process.
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