Catalytic oxidation of olefins with Pd(II) complexes has generated considerable controversy concerning the stereochemistry of hydroxypalladation (mode of addition of Pd(II) and OH to the olefin double bond). Several mechanistic and stereochemical probes were designed and applied to gain a more detailed insight into the stereochemistry of hydroxpalladation. Results showed that the mode of addition is different under different reaction conditions. Thus, Wacker reaction of olefins proceeds through two possible mechanistic pathways: 1) anti-oxypalladation; or 2) syn-oxypalladation. The results were confirmed by a stereochemical probe involving chirality transfer. These results were the initiative in designing new asymmetric synthetic tools for the formation of optically active chlorohydrins, �-substitued ketones, and optically active diesters containing three contiguous chiral centers shown in the following scheme. In the current presentation an overview of all the mechanistic and stereochemical tools that are in support of the dependence of the mode hydroxypalladation addition on the reaction conditions will be presented. 

Stereochemical and mechanistic probes for understanding the stereoselectivity of addition to alkenes in the Wacker reaction

243rd National Meeting (2012)

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