Organometallic compounds with 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. 

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

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... 

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

The treatment of organometallic compounds with appropriate haloorganostan-nanes affords unsymmetrical tetraorganotin compounds (eq (131)) [126]. By the use of Reformatsky reagents and metal enolates, a-trialkylstannyl esters and ketones are obtained, respectively. 

In addition to trialkylboranes, various alkoxyboron compounds have prominent roles in synthesis. Some of these, such as catecholboranes (see. p. 340) can be made by hydroboration. Others are made by organometallic or related substitution reactions. Alkoxyboron compounds are usually named as esters. Compounds with one alkoxy group are esters of borinic acids and are called borinates. Compounds with two alkoxy groups are called boronates. Trialkoxyboron compounds are borates. 

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... 

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