Ruthenium-Catalyzed Decarboxylative Insertion of Electrophiles A ruthenium complex, Cp*Ru(bipyridyl)Cl, has been developed as a catalyst for the first regioselective tandem Michael addition  allylic alkylation of activated Michael acceptors. The net transformation is the decarboxylative insertion of Michael acceptors into allyl â-ketoesters. Org. Lett., Vol. 7, No. 11, 2005

Ruthenium-Catalyzed Decarboxylative Allylation of Nonstabilized Ketone Enolates Bipyridyl(pentamethylcyclopentadienyl)ruthenium chloride is an efficient catalyst for the formal [3,3] rearrangement of allyl β-ketoesters. The mechanism of the transformation involves formation of π-allyl ruthenium intermediates, which are selectively attacked at the more substituted allyl terminus by freely diffusing enolates. Decarboxylation of β － ketocarboxylates allows generation of enolates under extremely mild conditions. Org. Lett., Vol. 6, No. 15, 2004

General procedure for catalytic Carroll rearrangements: In a Schlenk tube under argon, [Cp*RuCl]4 (2.5 mol %) and bipyridine (10 mol %) were dissolved in 2 mL of methylene chloride. The resulting deep purple solution was allowed to stir briefly before addition of allyl-β-ketoester (1 mmol) in 3 mL of methylene chloride via cannula. The reaction was allowed to stir under Ar until the resulting dark burnt orange solution returned to purple.

Formation of Aryl-Nitrogen, Aryl-Oxygen, and Aryl-Carbon Bonds Using Well-Defined Copper(I)-Based Catalysts These complexes are soluble in organic solvents such as dichloromethane,chloroform, toluene (warm), benzene, NMP, DMF,and DMSO. However, they are insoluble in diethyl ether or hexane. Unlike soluble copper(I) salts such as copper triflate, 1 and 2 are stable to air and ambient moisture.

Org. Lett., Vol. 3, No. 26, 2001

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