Unusual Allylpalladium Carboxylate Complexes: Identification of the Resting State of Catalytic Enantioselective Decarboxylative Allylic Alkylation Reactions of Ketones

Creators: Sherden, Nathaniel H.; Behenna, Douglas C.; Virgil, Scott C.; Stoltz, Brian M.

Abstract

Palladium pop rocks: Hold on to your CO2! Enantioselective palladium-catalyzed decarboxylative alkylation of ketone enolates proceeds via 1-σ-allyl palladium-carboxylate complexes, such as 1 (Pd yellow, O red, N blue, P purple), by slow loss of CO_2. Reminiscent of pop rock candy, impure samples of 1 expel a gas (presumably CO_2) in the solid state and effervesce in solution.

Additional Information

Copyright © 2009 WILEY-VCH. Received: 14 May 2009; Revised: 5 July 2009. Published Online: 11 August 2009. We thank NIH-NIGMS (R01 GM 080269-01), Abbott Laboratories, Amgen, Merck, Bristol-Myers Squibb, Boehringer Ingelheim, the Fannie and John Hertz Foundation (predoctoral fellowship to DCB), the Gordon and Betty Moore Foundation, and Caltech for financial support. Lawrence Henling and Dr. Michael Day are gratefully acknowledged for X-ray crystallographic structural determination. The Bruker KAPPA APEX II X-ray diffractometer was purchased through an NSF CRIF:MU award to the California Institute of Technology, CHE-0639094. Prof. J. E. Bercaw, Prof. R. H. Grubbs, Prof. S. E. Reisman, Prof. W. A. Goddard III, and Dr. J. A. Keith are acknowledged for helpful discussions. Dr. David Vander Velde and Dr. Scott Ross are thanked for helpful assistance related to NMR.

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