Xavier Tania, Condon Sylvie, Pichon Christophe, Le Gall Erwan, Presset Marc
Université Paris Est Créteil, CNRS, ICMPE, 2 rue Henri Dunant, F-94320 Thiais, France.
Beilstein J Org Chem. 2021 Aug 18;17:2085-2094. doi: 10.3762/bjoc.17.135. eCollection 2021.
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.
单取代丙二酸半酯（SMAHOs）的应用因关于其制备的文献记载零散而受到阻碍。我们对不同方法进行了评估，从而确定了在丙二酸位置和酯官能团上引入多样性的最佳策略。通过卤代烃对丙二酸酯进行经典的烷基化步骤，然后进行单皂化反应，可得到在丙二酸位置带有不同取代基的试剂，包括官能化衍生物。另一方面，事实证明，取代丙二酸衍生物的单酯化步骤是在酯官能团上实现多样性的最佳途径，而不是使用中间体麦氏酸。这两种转化都具有简单高效的特点，能够直接从廉价的起始原料制备SMAHOs。
