Cicco Luciana, Sblendorio Stefania, Mansueto Rosmara, Perna Filippo M, Salomone Antonio, Florio Saverio, Capriati Vito
Dipartimento di Farmacia-Scienze del Farmaco , Università di Bari "Aldo Moro" , Consorzio C.I.N.M.P.I.S. , Via E. Orabona 4, I-70125 , Bari , Italy . Email:
Chem Sci. 2016 Feb 1;7(2):1192-1199. doi: 10.1039/c5sc03436a. Epub 2015 Nov 3.
It has always been a firm conviction of the scientific community that the employment of both anhydrous conditions and water-free reaction media is required for the successful handling of organometallic compounds with highly polarised metal-carbon bonds. Herein, we describe how, under heterogeneous conditions, Grignard and organolithium reagents can smoothly undergo nucleophilic additions to γ-chloroketones, on the way to 2,2-disubstituted tetrahydrofurans, "on water", competitively with protonolysis, under batch conditions, at room temperature and under air. The reactivity of the above organometallic reagents has also been investigated in conventional anhydrous organic solvents and in bio-based eutectic and low melting mixtures for comparison. The scope and limitations of this kind of reaction are discussed.
科学界一直坚信，为了成功处理具有高度极化金属 - 碳键的有机金属化合物，需要采用无水条件和无水溶液反应介质。在此，我们描述了在多相条件下，格氏试剂和有机锂试剂如何在室温及空气中的间歇条件下，与质子解反应竞争，在“水相”中顺利地对γ - 氯代酮进行亲核加成反应，生成2,2 - 二取代四氢呋喃。为作比较，还研究了上述有机金属试剂在传统无水有机溶剂以及生物基低共熔混合物和低熔点混合物中的反应活性。讨论了这类反应的适用范围和局限性。
