Regioselective synthesis, structure and behavior in solutions of novel phosphorylated thiazolidin-4-ones

✍ Scribed by Vladimir A. Kozlov; Irina L. Odinets; Konstantin A. Lyssenko; Svetlana G. Churusova; Sergey V. Yarovenko; Pavel V. Petrovskii; Tatyana A. Mastryukova

• Publisher: John Wiley and Sons
• Year: 2005
• Tongue: English
• Weight: 156 KB
• Volume: 16
• Category: Article
• ISSN: 1042-7163
• DOI: 10.1002/hc.20084

✦ Synopsis

Abstract

Regioselective syntheses of novel 2‐(phosphoryl)methylidenethiazolidine‐4‐ones 3a–c, 5 by the condensation of phosphoryl acetic acid thioamides 2a–c or substituted thioanilide 4 with dimethyl acetylenedicarboxylate are described. N^3^‐unsubstituted thiazolidine‐4‐ones 3a–c were obtained as E,Z‐isomers, while N^3^‐phenyl substituted heterocycle 5 was formed as Z,Z‐isomer. The structures of thiazolidin‐4‐ones 3a‐E,Z and 5‐Z,Z are characterized by crystal structure determination. According to B3Pw91/6‐31G* calculations, the isomers observed in crystals are thermodynamically preferable. In solutions, phosphorylated thiazolidines undergo isomerization (relative to C^2^ carbon atom of the heterocycle) proceeded by either imine–enamine (N^3^‐unsubstituted compounds 3a–c) or push–pull mechanisms (N^3^‐substituted compound 5). © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:159–222, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20084