Organometallic compounds esters

For a list of preparations of ketones by the reaction of organometallic compounds with carboxylic esters, salts, anhydyrides, or amides, with references, see Ref. 568, pp. 685, 693. 

The Conversion of Organometallic Compounds to Ketones, Aldehydes, Carboxylic Esters, or Amides... 

Coupling of Organometallic Compounds with Aryl Halides, Ethers, and Carboxylic Esters... 

Organometallic compounds or carbanions undergo a number of reactions in which the carbanion or carbanion-like moiety of the organometallic compound acts as a nucleophilic displacing agent. Examples are the formation of hydrocarbons from alkyl halides, alkyl halides from halogens, and ketones from acid chlorides or esters. The latter two reactions are closely related to the base-catalyzed condensations and are perhaps additions as well as displacement reactions. Related addition reactions are the carbonation of organometallic compounds and the addition to ketones or aldehydes. 

Ethyl 2,3-epoxypropanoate is a very interesting chiron. It may be opened by various organometallic compounds such as dialkyl, diaryl, and divinyl lithium cuprates, dialkylmagnesium cuprates, trialkylalanes and aluminum acetylides.5 6 The epoxide ring is attacked regiospecifically at the p-position and produces a-hydroxy esters exclusively without racemization. The same result is observed with... 

Interest in the uses of HMPT has also been maintained, but a warning has been issued (by the E. I. du Pont de Nemours Company and the U.S. National Institute for Occupational Safety and Health) about its potential acute toxicity. HMPT has been used in the synthesis of 2,4-bis(dimethylamino)qui nolines,9 8 as a solvent for reactions between carbonyl compounds and sulphur," for the conversion of iV-benzylcarbox-amides into 3-phenylpropionitriles,100 in reactions between metals or organometallic compounds with a variety of organic substrates,101 and as a solvent for alkylation reactions of /J-keto-esters and related compounds in which the alkylation reaction is accompanied by de(alkoxycarbonylation) (Scheme 7).102... 

For some monomers (e.g., nitroethylene and 2-cyano-2,4-hexadienoic acid ester, CH3-CH=CH-CH=C(CN)-COOR), anionic polymerization can be conducted in aqueous alkaline solution. Other anionic initiators are Lewis bases, e.g., tertiary amines or phosphines, and organometallic compounds (see Sect. 3.2.1.2). Since the polarizability of unsaturated compounds depends very much on the substituents and on the solvent used, there are considerable differences in the effectiveness of the initiators mentioned. 

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. 

For reviews of ihc reaction between organometallic compounds and CO . see Volpin Kolomnikov Or a/iomet. React. 1975, 5. 313-386 Snecden. in Patai The Chemistry of Carboxylic Acids and Esters, Wilev New York. 1969, pp. 137-173 Kharasch Rcinmuih. Ref. 351. pp. 913-948. Fora more general review, see Lupidus Ping Russ. Chetn. Ret. 1981, 50. 63-75. 

Coupling of organometallic compounds with aryl halides, ethers, and esters... 

Addition of organometallic compounds to unsaturated esters 5-20 Addition of tin and mercury hydrides to unsaturated ketones 5-22 Free-radical addition of carboxylic esters to olefins... 

Unsaturated Nitriles, Nitro Compounds, and Sulfonic Acids and Esters 2-33 Cyanation of vinylic organometallic compounds... 

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