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. 2012 Nov 12;51(46):11505-9.
doi: 10.1002/anie.201206702. Epub 2012 Oct 16.

Reconciling the stereochemical course of nucleopalladation with the development of enantioselective wacker-type cyclizations

Adam B Weinstein  1 , Shannon S Stahl
Affiliations

Reconciling the stereochemical course of nucleopalladation with the development of enantioselective wacker-type cyclizations

Adam B Weinstein et al. Angew Chem Int Ed Engl. .

Abstract

A novel stereochemical substrate probe was used to assess the factors that affect the stereochemical course of nucleopalladation (cis vs. trans) in the context of an enantioselective Wacker-type reaction. We demonstrate that 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.

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Figures

Scheme 1
Scheme 1
Stereochemical pathways for alkene nucleopalladation.
Scheme 2
Scheme 2
Cyclization of substrate 3-D-4 with chiral catalyst.
Scheme 3
Scheme 3
(A) Mechanistic pathways for the reaction of 6-D-1 and (B) mathematical relationships used to determine the yields of products A–D.
Scheme 4
Scheme 4
Experimental data and trans:cis-AP selectivity obtained from oxidative cyclization of substrate 6-D-1 with the optimized chiral catalyst conditions.
Scheme 5
Scheme 5
Experimental data and trans:cis-AP selectivity obtained from oxidative cyclization of substrate 6-D-1 with a Pd(pyrox)(OAc)2 catalyst system (refer to Scheme 4 for depiction of the reaction).
See this image and copyright information in PMC

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