The transition metal-catalyzed cross-coupling of aryl electrophiles (i.e. –Br, –Cl, –OTf) with substituted Corey-Seebach <i>umpolung</i> reagents is described. Recently we disclosed the first examples of palladium-catalyzed cross-couplings of 2-aryl-1,3-dithianes with aryl bromides. Wanting to increase the utility of the transformation, we now report the first use of alternative electrophiles including aryl chlorides and triflates. Critical to expanding electrophile scope was the modification of our catalyst system. We found that the use of the third generation biphenyl Buchwald catalyst system engaged previously unreactive aryl triflates. Additionally we found aryl chlorides would react when moving to a nickel-based catalyst. The expanding reaction scope, our group's current mechanistic understanding, and future goals are presented.

Expansion of electrophile scope in the transition metal-catalyzed coupling of Corey-Seebach <i>umpolung</i> reagents

249th National Meeting (2015)

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Expansion of electrophile scope in the transition metal-catalyzed coupling of Corey-Seebach umpolung reagents