SYNTHESES OF NITRILE AND METHYL ESTER CORRESPONDING TO (dl)-SARKOMYCIN AND OF RELATED COMPOUNDS.

Article abstract of DOI:10.1016/S0040-4020(01)89959-2

Nitrile 6a and ester 12 corresponding to (dl)-sarkomycin, 6- and 7-membered rings analogue nitriles 6b, 6c, and 3-methyl substituted nitrile 6d were prepared.Conjugate addition of cyanotrimethyl silane to cyclic α-enones gave 3-trimethylsiloxy 2-cycloalkene carbonitriles.Their alkylation with chloromethyl phenyl sulfide followed by oxone oxidation to sulfones and sulfinic acid elimination on basic alumina led to α-methylene carbonyl compounds.Obtention of the ester 12 involved acetalization of 3-oxo 2-phenylthiomethyl cyclopentane carbonitrile, basic hydrolysis into acid, deacetalization, esterification, oxidation and elimination of sulfinic acid.