ChemInform Abstract: Aerobic Oxidative Coupling Between Carbon Nucleophiles and Allylic Alcohols: A Strategy to Construct β-(Hetero)aryl Ketones and Aldehydes Through Hydrogen Migration.

ChemInform ◽  
2014 ◽  
Vol 45 (18) ◽  
pp. no-no
Author(s):  
Liangbin Huang ◽  
Ji Qi ◽  
Xia Wu ◽  
Wanqing Wu ◽  
Huanfeng Jiang
Keyword(s):  
Oxidative Coupling ◽  
Allylic Alcohols ◽  
Hydrogen Migration ◽  
Carbon Nucleophiles ◽  
Aryl Ketones

scholarly journals Palladium-catalyzed alkylation of unactivated olefins

2004 ◽  
Vol 76 (3) ◽  
pp. 671-678 ◽  
Author(s):  
Ross A. Widenhoefer
Keyword(s):  
Good Yield ◽  
Catalytic Amount ◽  
Outer Sphere ◽  
Deuterium Labeling ◽  
Carbon Nucleophiles ◽  
Keto Esters ◽  
Reactive Carbon ◽  
Aryl Ketones ◽  
Palladium Catalyzed ◽  
Hydride Elimination

The reaction of a 3-butenyl β-diketone with a catalytic amount of PdCl2(CH3CN)2 in dioxane at room temperature led to olefin hydroalkylation and formation of the corresponding 2-acylcyclohexanone in good yield as a single regioisomer. Deuterium-labeling experiments for the hydroalkylation of 7-octene-2,4-dione were in accord with a mechanism involving outer-sphere attack of the pendant enol on a palladium-complexed olefin to form a palladium cyclohexyl species, followed by palladium migration via iterative β-hydride elimination/addition and protonolysis from a palladium enolate complex. In comparison to a 3-butenyl β-diketone, reaction of a 4-pentenyl β-diketone with a catalytic amount of PdCl2(CH3CN)2 in the presence of CuCl2 led to oxidative alkylation and formation of the corresponding 2-acyl-3-methyl-2-cyclohexenone in good yield as a single isomer. Unactivated olefins tethered to less reactive carbon nucleophiles such as β-keto esters, α-aryl ketones, and even dialkyl ketones underwent palladium-catalyzed hydroalkylation in the presence of Me3SiCl or HCl to form the corresponding cyclohexanones in moderate-to-good yield with high regioselectivity.

Oxidative Coupling of Aryl Boron Reagents with sp3-Carbon Nucleophiles: The Enolate Chan-Evans-Lam Reaction

2016 ◽  
Vol 55 (5) ◽  
pp. 1894-1898 ◽  
Author(s):  
Patrick J. Moon ◽  
Heather M. Halperin ◽  
Rylan J. Lundgren
Keyword(s):  
Oxidative Coupling ◽  
Carbon Nucleophiles
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