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Synlett 2022; 33(17): 1751-1755
DOI: 10.1055/a-1892-9911
DOI: 10.1055/a-1892-9911
letter
Dynamic Kinetic Resolution of Azlactones by Bifunctional Thioureas with α‑Trifluoromethyl or Methyl Groups
We thank the Dirección General de Asuntos del Personal Académico, Universidad Nacional Autónoma de México (DGAPA-UNAM) (Project no. IN209915) and the Consejo Nacional de Ciencia y Tecnología (CONACyT) (Grant no. 254014) for financial support. E.I.J., M.C.-R. and H.D.-S. gratefully acknowledge CONACyT, México for Ph.D. scholarships (Nos. 336875, 271149 and 576662, respectively). We are also thankful to LANCAD-UNAM-DGTIC-252 for supercomputer time.
Abstract
The asymmetric ring opening of azlactones via dynamic kinetic resolution (DKR) is investigated by contrasting thioureas incorporating 1-arylethyl substituents against their more acidic trifluoromethylated analogs. All the catalysts under study outperform Takemoto’s thiourea because of the inclusion of an additional chiral center. However, the difference in yield and selectivity between the fluorinated and non-fluorinated catalysts is minimal. We explain this observation by analysis of calculated transition states. Our findings show that the hydrogen bond (HB) between the NH linked to the 1-arylethyl and the negatively charged oxygen in the benzyloxy ion is the longest in the HB network, whereas the HB between the ammonium group and the same oxygen atom is the shortest. Thus, the substituents and the HB donor ability of this chiral fragment attached to the thiourea are not important in the reaction.
Key words
amino acids - asymmetric catalysis - stereoselectivity - kinetic resolution - asymmetric synthesisSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1892-9911.
- Supporting Information
Publication History
Received: 14 June 2022
Accepted after revision: 06 July 2022
Accepted Manuscript online:
06 July 2022
Article published online:
29 July 2022
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References and Notes
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