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Heterogeneous versus homogeneous palladium catalysts for ligandless mizoroki-heck reactions: a comparison of batch/microwave and continuous-flow processing.
MedLine Citation:
PMID:  19086042     Owner:  NLM     Status:  PubMed-not-MEDLINE    
Abstract/OtherAbstract:
Mizoroki-Heck couplings of aryl iodides and bromides with butyl acrylate were investigated as model systems to perform transition-metal-catalyzed transformations in continuous-flow mode. As a suitable ligandless catalyst system for the Mizoroki-Heck couplings both heterogeneous and homogeneous Pd catalysts (Pd/C and Pd acetate) were considered. In batch mode, full conversion with excellent selectivity for coupling was achieved applying high-temperature microwave conditions with Pd levels as low as 10(-3) mol %. In continuous-flow mode with Pd/C as a catalyst, significant Pd leaching from the heterogeneous catalyst was observed as these Mizoroki-Heck couplings proceed by a homogeneous mechanism involving soluble Pd colloids/nanoparticles. By applying low levels of Pd acetate as homogeneous Pd precatalyst, successful continuous-flow Mizoroki-Heck transformations were performed in a high-temperature/pressure flow reactor. For both aryl iodides and bromides, high isolated product yields of the cinnamic esters were obtained. Mechanistic issues involving the Pd-catalyzed Mizoroki-Heck reactions are discussed.
Authors:
Toma N Glasnov; Silvia Findenig; C Oliver Kappe
Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  Chemistry (Weinheim an der Bergstrasse, Germany)     Volume:  15     ISSN:  1521-3765     ISO Abbreviation:  Chemistry     Publication Date:  2009  
Date Detail:
Created Date:  2009-01-14     Completed Date:  2009-02-24     Revised Date:  2009-08-04    
Medline Journal Info:
Nlm Unique ID:  9513783     Medline TA:  Chemistry     Country:  Germany    
Other Details:
Languages:  eng     Pagination:  1001-10     Citation Subset:  -    
Affiliation:
Christian Doppler Laboratory for Microwave Chemistry (CDLMC) and Institute of Chemistry, Karl-Franzens-University Graz, Heinrichstrasse 28, 8010 Graz, Austria.
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