General Synthesis and Reactions

General Synthesis and Reactions.—Linear primary alcohols with at least seven carbon atoms are transformed into esters in high yield using copper oxide at temperatures above 170 C in the liquid phase. RusfCO) catalyses the conversion of an aldehyde, or an alcohol with the same number of carbon atoms, into an ester in the presence of diphenylacetylene. The carbonylation of organic halides in the presence of cyclic ethers is catalysed by PhPdI(PPh3)2 , it provides a synthesis of halohydrin esters in reasonable yield. Cyanohydrin esters have been synthesized by the sodium borohydride reduction of acyl cyanides in the presence of tetra-n-butylammonium bromide.  

Berthon, A. Forestiere, G. Leleu, and B. Sillion, Tetrahedron Lett., 1981, 22, 4073. 

Rh (CO)i6 is a highly active catalyst in the reaction of ethyl diazoacetate with alkenes to give cyclopropyl esters. Yields obtained are better than those obtained using palladium and copper catalysts. Methyl ester derivatives of tricyclo[4.2.0.0 ]octane have been prepared by a photochemical Wolff rearrangement of a related diazoketone in methanol.  

Schmierer, G. Grotemeier, G. Helmchen, and A. Selim, Angew. Chem., Int. Ed. Engl., 1981, 

Reagents i, EtjN-ZnClj-MejSiCl ii, LDA iti, MeaSiCl iv, MeC(OMe)3-TiCl4 

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General Synthesis and Reactions of Esters.— Esters and lactones are formed from ketones under aprotic conditions, using bis(trimethylsilyl) peroxide and a catalytic amount of trimethylsilyl trifluoromethanesulphonate yields for ten examples are between 24 and 76%. The reaction occurs specifically at the carbonyl group and carbon-carbon double-bonds are not affected. " Aldehydes are converted into methyl esters with a solution of sodium hypochlorite and methanol in acetic add yields of between 22 and 90% are obtained for seven examples. A similar reaction involves the treatment of an aldehyde with t-butyl hypochlorite followed by an alcohol yields are between 39 and 98% for six examples (Scheme 34). ... 

General Synthesis and Reactions of Esters Synthesis of Diesters Synthesis of Hydroxy-esters Synthesis of Keto-esters Synthesis of Unsaturated Esters Synthesis of Aromatic Esters Synthesis of Thioesters Synthesis of Vinylogous Esters... 

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