Hydrodehalogenation of Aryl Chlorides and Aryl Bromides Using a Microwave-Assisted, Copper-Catalyzed Concurrent Tandem Catalysis Methodology

Autor:	Amy H. Roy MacArthur, Meagan E. Geuther, Colin K. Kelly, Kathleen A. Cannon, Shirley Lin
Rok vydání:	2011
Předmět:	chemistry.chemical_classification Concurrent tandem catalysis Aryl Organic Chemistry Medicinal chemistry Catalysis Inorganic Chemistry Solvent chemistry.chemical_compound Hydrocarbon Catalytic cycle chemistry Diamine Organic chemistry Physical and Theoretical Chemistry Acetonitrile
Zdroj:	Organometallics. 30:4067-4073
ISSN:	1520-6041 0276-7333
DOI:	10.1021/om2003706
Popis:	A concurrent tandem catalytic methodology has been developed for the hydrodehalogenation of aryl bromides and aryl chlorides. The first step of the tandem catalytic cycle, halogen exchange, produced yields of 84–97% from aryl bromides using 5 mol % CuI catalyst, 10 mol % N,N′-dimethylcyclohexane-1,2-diamine (1), and 2 equiv of NaI in acetonitrile under microwave radiation at 100 °C in 0.5–1.5 h. The same reaction for aryl chlorides appeared to be equilibrium-limited after 1 hour at 200 °C (yields of 5–44%). Both aryl bromides and aryl chlorides were hydrodehalogenated in 12–87% yield using 20 mol % CuI, 1.5 equiv of diamine 1, and 2 equiv of NaI in acetonitrile at 200 °C after 1–2 h. Substrates with oxygen- or nitrogen-containing functional groups had substantially lower yields than hydrocarbon substrates. Deuterium labeling studies suggest that diamine 1 supplies the majority of the hydrogen for the hydrodehalogenation reaction, but solvent can also serve as a source.
Databáze:	OpenAIRE
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