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Reconciling the Stereochemical Course of Nucleopalladation with the Development of Enantioselective Wacker-Type Cyclizations


  • We thank Dr. Richard I. McDonald and Chun Pong Tam for initiating the synthesis of substrate probe 6-D-1, and Paul B. White and Dr. Charlie G. Fry for assistance with NMR spectroscopic measurements. We thank the NIH (R01 GM67163) and Organic Syntheses (ACS Division of Organic Chemistry fellowship for A.B.W.) for financial support of this work. Spectroscopic instrumentation was partially funded by the NSF (CHE-0342998, CHE-9629688, CHE-9208463) and NIH (1 S10 RR13866-01).


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A stereochemical substrate probe was used to assess the factors that affect the stereochemical course of nucleopalladation in the context of an enantioselective Wacker-type reaction. The enantioselectivity correlates directly with the nucleopalladation pathway, and both the neutral-donor and anionic ligands on palladium are capable of controlling selectivity for cis- or trans-nucleopalladation (see scheme; TFA=trifluoroacetate).

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