Methyl cyanoformate synthesis

Synthesis of p-Ketoesters by C-Acylation of Preformed Enolates with Methyl Cyanoformate Preparation of (la,4ag,8ao)Methyl 2-Oxo-decahydro-l-naphthoate... 

More recently, Hoppe et all63 also reported a stereoselective synthesis of a P -amino-u -hydroxy enone and its transformation to a 1,2-dihydroxyethylene isostere (Scheme 29). The addition of dilithium dimethylcyanocuprate to the conjugated C=C bond proceeds smoothly to produce a Z-enolate. The C-methoxycarbonylation with methyl cyanoformate forms the epimeric mixture of the 3-oxo ester. The product is then reduced with sodium cyanobo-rohyde to provide a protected form of the 1,2-dihydroxyethylene isostere. 

SYNTHESIS OF p-KETO ESTERS BY C-ACYLATION OF PREFORMED ENOLATES WITH METHYL CYANOFORMATE PREPARATION OF METHYL (1a,4ap,8aa)-2-OXODECAHYDRO-1-NAPHTHOATE... 

TRIFLUORO-2-BUTYNOATE. C-Acylation of an enolate using methyl cyanoformate provides a convenient source of the a-carbometh-oxyoctalone, METHYL (la,4Ap,8Aa)-2-OXO-DECAHYDRO-l-NAPH-THOATE and represents a good example of generating jS-keto esters under mild conditions. The nitrone functionality is featured in a procedure which makes it in a single step from secondary amines and 6-METHYL-2,3,4,5-TETRAHYDROPYRIDINE N-OXIDE is the example described. Finally, the synthesis of phospholes l-PHENYL-2,3,4,5-TETRAMETHYLPHOS-PHOLE is described as an example of the versatility of zirconocene chemistry. 

Crabtree S. R. Mander, L. N. Sethi, S. R Synthesis of (3-Keto Esters by C-Acylation of Preformed Enolates with Methyl Cyanoformate Preparation of Methyl (la,4ap,8aa)-2-oxodecahydro-l-naphthoate OS, (1991), 70, 256. 

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