Ruthenium(II)-Catalyzed C–H Bond Activation and Functionalization

Ru-, Rh-, and Pd-Catalyzed C-C Bond Formation Involving C-H Activation and Addition on Unsaturated Substrates: Reactions and Mechanistic Aspects

The cleavage and addition of ortho C−H bonds in various aromatic compounds such as ketones, esters, imines, imidates, nitrile, and aldehydes to olefins and acetlylenes can be achieved catalytically with the aid of ruthenium catalysts. The reaction is generally highly efficient and useful in synthetic methods. The coordination to the metal center by a heteroatom in directing groups such as carbonyl and imino groups is the key. The reductive elimination to form a C−C bond is the rate-determining step.

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Catalytic C−H/Olefin Coupling

Alkylation reactions represent an important organic transformation to form C–C bonds. In addition to conventional approaches with alkyl halides or sulfonates as alkylating agents, the use of unactivated olefins for alkylations has become attractive from both cost and sustainability viewpoints. This Review summarizes transition-metal-catalyzed alkylations of various carbon–hydrogen bonds (addition of C–H bonds across olefins) using regular olefins or 1,3-dienes up to May 2016. According to the mode of activation, the Review is divided into two sections: alkylation via C–H activation and alkylation via olefin activation.

Transition-Metal-Catalyzed C–H Alkylation Using Alkenes

Non-Metathesis Ruthenium-Catalyzed C−C Bond Formation

The reaction of aromatic nitriles with triethoxyvinylsilane proceeded in the presence of a Ru(H)2(CO)(PPh3)3-catalyst to give the corresponding C-H/olefin coupling products in high yields. The nitrile group is capable of directing the ruthenium to the ortho C-H bond via π-bonded mode.

The Ruthenium-Catalyzed Addition of C-H Bonds in Aromatic Nitriles to Olefins

Catalyst-specific C-H/olefin as well as C-H/acetylene coupling has been accomplished for aromatics which contain both keto and imino substituents by simply changing the catalyst. By using Ru(H)2(CO...

New Protocol for the Siteselective Alkylation and Vinylation of Aromatic Compounds. Catalyst-Specific Reactions

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Takuya Tsujimoto

Papers

The Ruthenium-Catalyzed Addition of C-H Bonds in Aromatic Nitriles to Olefins

New Protocol for the Siteselective Alkylation and Vinylation of Aromatic Compounds. Catalyst-Specific Reactions

The Transition Metal-Catalyzed Addition of C-H Bonds in Aromatic Hydrazones to Olefins

The Ruthenium-Catalyzed Addition of C—H Bonds in Aromatic Nitriles to Olefins.

New Protocol for the Siteselective Alkylation and Vinylation of Aromatic Compounds. Catalyst‐Specific Reactions.