Substituent Effects on [1,3]-Rearrangement of Alkynyl S,N-Acetals to 1- Amino-3-Sulfenylallenes and their Conversion to α,β-Unsaturated Ketones

Title: Substituent Effects on [1,3]-Rearrangement of Alkynyl S,N-Acetals to 1- Amino-3-Sulfenylallenes and their Conversion to α,β-Unsaturated Ketones

Volume: 3 Issue: 5

Author(s): Toshiaki Murai, Yuichiro Mutoh and Kozue Fukushima

Affiliation:

Keywords: Thioamides, alkynyl S,N-acetals, [1,3]-rearrangement, 1-amino-3-sulfenylallenes, substituent effects, a,b-unsaturated ketones

Abstract: The reaction of thioiminium salts derived from aromatic thioamides with lithium phenylacetylide exclusively gave S,N-acetals, whereas the reaction with lithium (trimethylsilyl)acetylide gave 1-amino-3- sulfenylallenes via [1,3]-rearrangement. The easiness of [1,3]-rearrangement was highly dependent on the substituents at the nitrogen atom. Chromatographic purification of the reaction mixture produced α,β- unsaturated ketones.

Cite this article as:

Murai Toshiaki, Mutoh Yuichiro and Fukushima Kozue, Substituent Effects on [1,3]-Rearrangement of Alkynyl S,N-Acetals to 1- Amino-3-Sulfenylallenes and their Conversion to α,β-Unsaturated Ketones, Letters in Organic Chemistry 2006; 3 (5) . https://dx.doi.org/10.2174/157017806776611872