1603833-11-9Relevant academic research and scientific papers
Synthesis of Monothiomalonates – Versatile Thioester Enolate Equivalents for C–C Bond Formations
Engl, Oliver D.,Saadi, Jakub,Cosimi, Elena,Wennemers, Helma
, (2017/12/01)
Monothiomalonates (MTMs) are surrogates of thioester enolates that allow for stereoselective C–C bond formations under mild conditions and thereby afford access to synthetically versatile thioester derivatives. Here we present a straightforward synthetic route to MTMs that proceeds through nucleophilic ring-opening of Meldrum's acid derivatives followed by O-alkylation of the resulting malonic acid half thioesters with alkyl triflates or acetimidates as electrophiles. The method affords MTMs in overall yields of 34?–?92% and allows for variations of the oxo- and thioester moieties as well as the substituent at the C(α) position.
Stereoselective metal-free synthesis of β-amino thioesters with tertiary and quaternary stereogenic centers
Bahlinger, Annette,Fritz, Sven P.,Wennemers, Helma
, p. 8779 - 8783 (2014/08/18)
β-Amino thioesters are important natural building blocks for the synthesis of numerous bioactive molecules. An organocatalyzed Mannich reaction was developed which provides direct and highly stereoselective access to acyclic β2- and β2,3,3-amino thioesters with adjacent tertiary and quaternary stereocenters. Mechanistic studies showed that the stereochemical course of the reaction can be controlled by the choice of the substrates. The β-amino thioesters were further functionalized by, for example, stereoselective decarboxylation to access β2,3- frameworks. In addition, the value of the β-amino thioesters was shown in coupling-reagent-free peptide synthesis.
