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

Sherden, Nathaniel H. and Behenna, Douglas C. and Virgil, Scott C. and Stoltz, Brian M. (2009) Unusual Allylpalladium Carboxylate Complexes: Identification of the Resting State of Catalytic Enantioselective Decarboxylative Allylic Alkylation Reactions of Ketones. Angewandte Chemie International Edition, 48 (37). pp. 6840-6843. ISSN 1433-7851. PMCID PMC2880474. https://resolver.caltech.edu/CaltechAUTHORS:20091012-124240065

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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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1002/anie.200902575DOIArticle
http://www3.interscience.wiley.com/journal/122543308/abstractPublisherArticle
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC2880474/PubMed CentralArticle
ORCID:
AuthorORCID
Virgil, Scott C.0000-0001-8586-5641
Stoltz, Brian M.0000-0001-9837-1528
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.
Funders:
Funding AgencyGrant Number
NIHR01GM080269-01
Abbott LaboratoriesUNSPECIFIED
AmgenUNSPECIFIED
MerckUNSPECIFIED
Bristol-Myers SquibbUNSPECIFIED
Boehringer-IngelheimUNSPECIFIED
Fannie and John Hertz FoundationUNSPECIFIED
Gordon and Betty Moore FoundationUNSPECIFIED
CaltechUNSPECIFIED
NSFCHE-0639094
Subject Keywords:allylic alkylation; asymmetric catalysis; carboxylate ligands; palladium; reaction mechanisms
Issue or Number:37
PubMed Central ID:PMC2880474
Record Number:CaltechAUTHORS:20091012-124240065
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20091012-124240065
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:16245
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:13 Oct 2009 20:22
Last Modified:09 Mar 2020 13:19

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