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Highly Regioselective Pd-Catalyzed Intermolecular Aminoacetoxylation of Alkenes and Evidence for cis-Aminopalladation and S_N2 C−O Bond Formation

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Guosheng Liu and Shannon S. Stahl*

Department of Chemistry, University of WisconsinMadison, 1101 University Avenue, Madison, Wisconsin 53706

J. Am. Chem. Soc., 2006, 128 (22), pp 7179–7181

DOI: 10.1021/ja061706h

Publication Date (Web): May 9, 2006

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, stahl@chem.wisc.edu

Abstract

Synthetic methods that achieve oxidative 1,2-difunctionalization of alkenes are very powerful in organic chemistry. Here we report the first examples of intermolecular Pd-catalyzed aminoacetoxylation of alkenes with phthalimide as the nitrogen source and PhI(OAc)₂ as the stoichiometric oxidant and source of acetate. These reactions are highly regio- and diastereoselective, and mechanistic studies reveal that the reaction proceeds via cis-aminopalladation of the alkene followed by oxidative cleavage of the intermediate Pd−C bond with inversion of stereochemistry.

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Published In Issue June 07, 2006
Received March 11, 2006

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Communication

Highly Regioselective Pd-Catalyzed Intermolecular Aminoacetoxylation of Alkenes and Evidence for cis-Aminopalladation and S_N2 C−O Bond Formation