Organometallic compounds esters, metal catalyzed

Three-component reactions between organic electrophile (halide, ester, etc.), carbon monooxide, and organic nucleophile (organometallic compound) (Equation (1)) catalyzed by transition metal complexes afford a powerful method for the synthesis of various ketones. The pioneering works in this area appeared in the early 1980s. 

Risse and S. Breunig, Transition metal catalyzed vinyl addition polymerizations of norbor nene derivatives with ester groups, Makromol. Chem. 193, 2915 (1992) C. Mehler and M. Risse, Addition polymerization of norbornene catalyzed by palladium(2- -) compounds. A polymerization reaction with rare chain transfer and chain termination, Macromol. 25, 4226 4228 (1992) R.G. Schulz, Polym. Lett. 4, 541 (1966). C. Tanielian, A. Kiennemann, and T. Osparpucu, Influence de differents catalyseurs abase d elements de transition du groupe VIII sur lapol3mierisation du norbor nene, Can. J. Chem. 57, 2022 (1979) A. Sen and T. W. Lai, Catalytic polymerization of acetylenes and olefins by tetrakis(acetonitrile)palladium(II) ditetrafluoroborate, Organometallics 1, 415 (1982) C. Mehler and W. Risse, Pd(II) catalyzed polymerization of norbornene derivatives, Mak romol. Chem. Rapid Commun. 12, 255 (1991). 

One important class of anionic-polymerization initiators are the organometallic compounds, especially those of lithium and sodium (see Chapter 5 to review the general properties of the metalloalkyls). Grignard reagents can induce polymerization of acrylonitrile and acrylate esters, but not of hydrocarbons. Initiation by organosodium compounds often involves in situ generation of the active species from sodium metal. Sodium metal catalyzes the polymerization of dienes, and the mechanism has been shown to involve a dianion formed by dimerization of the diene radical anion. An alternative initiation system for anionic polymerization involves... 

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