4(S)-Benzyl-1,3-thiazolidin-2-one a Novel Chiral Auxiliary for Asymmetric Aldol Coupling through Titanium Enolates

Authors

  • Dulce M. Mejia-Nuñez Universidad Autónoma del Estado de México
  • Salvador Mastachi-Loza Universidad Autónoma del Estado de México https://orcid.org/0000-0001-9772-0167
  • Diego Martinez-Otero Universidad Nacional Autónoma de México
  • Moises Romero-Ortega

DOI:

https://doi.org/10.29356/jmcs.v68i1.2067

Keywords:

Chiral auxiliaries, Coupling reaction, Stereoselective synthesis, Aldol adducts, Thiazolidinone

Abstract

The chlorotitanium enolate of N-propionyl-4(S)-benzyl-1,3-thiazolidin-2-one, was condensed with aryl aldehydes, in good diastereoselectivity to give the ‘Evans syn’ aldol (73:27 - 97:3), using equimolar amounts of titanium tetrachloride (1.5 equiv), and N,N-diisopropylethylamine (DIPEA). The facial selectivity in the aldol additions probably involves a non-chelated transition state. In all aldol reactions, the presence of a minor product, the ‘non-Evans syn’ aldol, was obtained and confirmed by X-ray diffraction analysis of a single-crystal compound containing the mixture of diastereoisomers. The chiral auxiliary in these 1,3-thiazolidin-2-one aldol derivatives can be easily removed by nucleophilic species through acyl substitution.

 

Resumen. El enolato de clorotitanio de N-propionil-4(S)-bencil-1,3-tiazolidin-2-ona, fue condensado con arilaldehídos, con buena diastereoselectividad produciendo el aldol “syn Evans” (73:27 - 97:3), utilizando cantidades equimolares de tetracloruro de titanio (1.5 equiv) y N,N-diisopropiletilamina (DIPEA). La selectividad facial en las adiciones aldólicas probablemente implica un estado de transición no-quelatado. En todas las reacciones aldólicas, la presencia de un producto minoritario, él aldol “non-Evans”, fue obtenido y confirmado por el análisis de difracción de rayos-X de monocristal de una mezcla de los diastereoisómeros. El auxiliar quiral en estos derivados de 1,3-tiazolidin-2-onas puede ser removido fácilmente por especies nucleofílicas a través de la sustitución del grupo acilo.

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Published

2024-01-01

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Special Issue dedicated to Prof. Joaquín Tamariz

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