Metal-catalyzed alcoholysis reactions

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... 

Mechanistic applications of the reactivity-selectivity principle, 14, 69 Mechanistic studies, heat capacities of activation and their use, 5, 121 Mechanistic studies on enzyme-catalyzed phosphoryl transfer, 40, 49 Medium effects on the rates and mechanisms of solvolytic reactions, 14, 1 Meisenheimer complexes, 7, 211 Metal-catalyzed alcoholysis reactions of... 

Brown RS, Neverov AA. Metal catalyzed alcoholysis reactions of carboxylate and organophosphoms esters. In Richard JP, ed. Advances in Physical Organic Chemistry. vol. 42. Elsevier 2007 271-331. 

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]. 

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). 

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. ... 

The alcoholysis of urea using alcohols and polyols has been known for a long time [76] to proceed in two quite distinct steps. Reaction (6.14), bearing to the urethane, at least with the lower homologues of the aliphatic alcohols, is a thermal reaction and does not require any catalyst [76-78]. The second step is a transition metal-catalyzed reaction. Ammonia formed in the two latter reactions can be recovered and reacted again with CO2 to reform urea, thus resulting in a net consumption of... 

The importance of a Si-H-M interaction in reaction intermediates was demonstrated in the studies of silane alcoholysis by an Ir complex (Eq. 2.29) [88]. Kinetic and mechanistic studies of silane alcoholysis catalyzed by [IrH2S2(PPh3)2]SbF6 (S = solvent) suggest that an unstretched silane 27 is an active intermediate. In this system the Ir(III) center carries a positive charge making the metal electrophilic. A Si-H bond coordinated to the electrophilic metal center would be activated without oxidative addition. The result is enhanced sensitivity to nucleophilic attack by... 

Brown RS, Neverov AA, Tsang JSW, Gibson GTT, Montoja-Pelaez PJ. Metal ion catalyzed acyl and phosphoryl transfer reactions to alcohols La -promoted alcoholysis of activated amides, carboxylate esters, and neutral organophosphorus esters. Can J Chem. 2004 82 1791-1805. 

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