Qiao Hui, Michalland Jean, Huang Qi, Zard Samir Z
Laboratoire de Synthèse Organique, CNRS UMR 7652, Ecole polytechnique, 91128, Palaiseau Cedex, France.
Chemistry. 2023 Oct 18;29(58):e202302235. doi: 10.1002/chem.202302235. Epub 2023 Sep 8.
A modular approach to highly functional acyl (MIDA)boronates is described. It involves the generation of the hitherto unknown radical derived from acetyl (MIDA)boronate and its capture by various alkenes, including electronically unbiased, unactivated alkenes. In contrast to the anion of acetyl (MIDA)boronate, which has not so far been employed in synthesis, the corresponding radical is well behaved and readily produced from the novel α-xanthyl acetyl (MIDA)boronate. This shelf-stable, easily prepared solid is a convenient acyl (MIDA)boronate transfer agent that provides a direct entry to numerous otherwise inaccessible structures, including latent 1,4-dicarbonyl derivatives that can be transformed into B(MIDA) substituted pyrroles and furans. A competition experiment indicated the acyl (MIDA)boronate substituted radical to be more stable than the all-carbon acetonyl radical but somewhat less reactive in additions to alkenes.
本文描述了一种用于高功能酰基（MIDA）硼酸酯的模块化方法。该方法涉及生成源自乙酰基（MIDA）硼酸酯的迄今未知的自由基，并通过各种烯烃捕获该自由基，包括电子中性、未活化的烯烃。与迄今尚未用于合成的乙酰基（MIDA）硼酸根阴离子不同，相应的自由基表现良好，并且很容易从新型α-黄原酰基乙酰基（MIDA）硼酸酯中产生。这种货架稳定、易于制备的固体是一种方便的酰基（MIDA）硼酸酯转移剂，可直接用于许多其他难以获得的结构，包括潜在的1,4-二羰基衍生物，这些衍生物可转化为B（MIDA）取代的吡咯和呋喃。竞争实验表明，酰基（MIDA）硼酸酯取代的自由基比全碳丙酮基自由基更稳定，但在与烯烃加成时反应性略低。
