3709-27-1Relevant articles and documents
Preparation of mono-substituted malonic acid half oxyesters (SMAHOs)
Condon, Sylvie,Le Gall, Erwan,Pichon, Christophe,Presset, Marc,Xavier, Tania
, p. 2085 - 2094 (2021/09/02)
The use of mono-substituted malonic acid half oxyesters (SMAHOs) has been hampered by the sporadic references describing their preparation. An evaluation of different approaches has been achieved, allowing to define the best strategies to introduce diversity on both the malonic position and the ester function. A classical alkylation step of a malonate by an alkyl halide followed by a monosaponification gave access to reagents bearing different substituents at the malonic position, including functionalized derivatives. On the other hand, the development of a monoesterification step of a substituted malonic acid derivative proved to be the best entry for diversity at the ester function, rather than the use of an intermediate Meldrum acid. Both these transformations are characterized by their simplicity and efficiency, allowing a straightforward access to SMAHOs from cheap starting materials.
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.
Mechanistic investigation of the selective reduction of Meldrum's acids to β-hydroxy acids using SmI2 and H2O
Szostak, Michal,Lyons, Sarah E.,Spain, Malcolm,Procter, David J.
supporting information, p. 8391 - 8394 (2014/07/22)
The mechanism of a recently reported first mono-reduction of cyclic 1,3-diesters (Meldrum's acids) to β-hydroxy acids with SmI 2-H2O has been studied using a combination of reactivity, deuteration, kinetic isotope and radical clock e