N-Bis(methylthio)methylene Derivatives. VII. Syntheses and Reactions of Synthetic Equivalents of New 1,3-Dipolar Reagents Using N-Bis(methylthio)methylene Derivatives

概要

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N-Cyano- or N-(p-toluenesulfonyl)-N'-(trimethylsilylmethyl)-S-methylisothioureas (3,4), readily prepared by reactions of S, S'-dimethyl N-cyano- (1a)b and S, S'-dimethyl N-(p-toluenesulfonyl)- (1b) carbonimidodithioates with trimethylsilylmethylamine (2a), followed by N-alkylation, have been found to provide synthetic equivalents of iminoazomethine ylide. Treatment of these compounds with cesium fluoride in the presence of reactive hetero-dipolarophiles such as carbonyl compounds afforded 1,3-dipolar cycloadducts, 4,5-dihydro-2-iminooxazoles and 4,5-dihydro-2-iminothiazoles, via the 1,3-elimination of (methylthio)trimethylsilane.S-Methyl-S'-trimethylsilylmethyl N-cyano- (5a) and N-(p-toluene-sulfonyl)- (5b) carbonimidodithioates, also readily prepared from the corresponding 1a and 1b with (mercaptomethyl)trimethylsilane (2b), were used as new reagents for introducing a thioformaldehyde unit at a carbonyl carbon. Reactions of these compounds with aldehydes in the presence of cesium fluoride afforded thiiranes via the 1,3-dipolar cycloaddition of iminothiocarbonyl ylide to the C=O double bond. Reactions of 5 with dimethyl fumarate and maleate in the presence of cesium fluoride in acetonitrile gave 1,3-dipolar cycloadducts, dimethyl 2-(N-(p-toluenesulfonyl)imino)tetrahydrothiophene-3,4-dicarboxylates.
公益社団法人日本薬学会の論文
1995-09-15