60179-38-6Relevant academic research and scientific papers
Preparation of mono-substituted malonic acid half oxyesters (SMAHOs)
Condon, Sylvie,Le Gall, Erwan,Pichon, Christophe,Presset, Marc,Xavier, Tania
supporting information, 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.
Decarboxylative ketone aldol reactions: Development and mechanistic evaluation under metal-free conditions
Blaquiere, Nicole,Shore, Daniel G.,Rousseaux, Sophie,Fagnou, Keith
supporting information; experimental part, p. 6190 - 6198 (2009/12/24)
(Chemical Equation Presented) Malonic acid half thioesters (MAHTs) and malonic acid half oxyesters (MAHOs) are shown to undergo decarboxylative nucleophilic addition reactions with ketone and aldehyde electrophiles in the presence of stoichiometric or catalytic quantities of triethylamine at room temperature. The ability to perform these reactions under metal-free conditions has enabled a detailed mechanistic analysis of the reaction pathway leading to the 1H NMR spectroscopic characterization of a postnucleophilic addition/predecarboxylation intermediate and experimental evidence for a reversible formation of this intermediate followed by an irreversible decarboxylation. Rate constants for each of the bond forming/bond breaking steps in the reaction pathway were also determined, casting light on the differing reactivity betweenMAHOandMAHT nucleophiles in these processes. Finally, the mechanistic insights gained through these studies have been employed in the development of a new decarboxylative coumarin synthesis.
Lanthanoid Complex as a Novel Carbon Dioxide Carrier for the Carboxylation of Active Methylene Compounds under Mild Conditions
Abe, Hiroshi,Inoue, Shohei
, p. 1197 - 1198 (2007/10/02)
A lanthanoid complex, formed by the addition of a lanthanoid alkoxide to an isocyanate, serves as a novel carbon dioxide carrier for the rapid carboxylation of active methylene compounds under mild conditions.
