Alcoholysis, metal catalyzed

Metal-catalyzed alcoholysis reactions of carboxylate and organophosphorus esters... 

Metal-catalyzed alcoholysis reactions of carboxylate and organophosphorus esters, 42, 271 Metal complexes, the nucleophilicity of towards organic molecules, 23, 1 Methyl transfer reactions, 16, 87... 

III. Metal-catalyzed esterification and alcoholysis reactions Influence of the structure of the reactants and of the nature of the reaction medium,J. Polym. Sci., Polym. Chem. Ed., 27, 3535-3550 (1989). 

These critical aspects of the classical fluorous biphasic catalysis led in recent works to the development of protocols for the conversions with modified catalyst systems in non-fluorinated hydrocarbons as solvents. As part of the BMBE lighthouse project, Gladyzs and coworkers appHed this concept to C - C coupHng reactions (Suzuki reaction) and other metal-catalyzed addition reactions (hydrosilylation, selective alcoholysis of alkynes), which have direct relevance for the synthesis of fine chemicals and specialties [74]. 

Transition metals have already established a prominent role in synthetic silicon chemistry [1 - 5]. This is well illustrated by the Direct Process, which is a copper-mediated combination of elemental silicon and methyl chloride to produce methylchlorosilanes, and primarily dimethyldichlorosilane. This process is practiced on a large, worldwide scale, and is the basis for the silicones industry [6]. Other transition metal-catalyzed reactions that have proven to be synthetically useful include hydrosilation [7], silane alcoholysis [8], and additions of Si-Si bonds to alkenes [9]. However, transition metal catalysis still holds considerable promise for enabling the production of new silicon-based compounds and materials. For example, transition metal-based catalysts may promote the direct conversion of elemental silicon to organosilanes via reactions with organic compounds such as ethers. In addition, they may play a strong role in the future... 

Reactions of the nitrile group(s) In general, these reactions start with a nucleophilic attack at the C atom of the nitrile group. Thus 10 reacted with its anion in basic media to yield the dimerization product 2-amino-1,1,3-tricyanopropene . Thiolysis with H2S gave cyanothioacetamide. Acidic alcoholysis in an neutral solvent produced dialkyl propanediimidate dihydrohalides Metal-catalyzed reactions of 10 with methyl acetoacetate and other j5-dicarbonyls have been reported. ... 

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