Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore.
Nat Commun. 2016 Oct 4;7:13024. doi: 10.1038/ncomms13024.
The Rauhut-Currier (RC) reaction represents an efficient method for the construction of carbon-carbon bond in organic synthesis. However, the RC reactions involving allenoate substrates are very rare, and in particular, asymmetric intramolecular RC reaction of allenoates is yet to be discovered. Here, we show that the intramolecular RC reaction proceeds smoothly in the presence of 1 mol% β-ICD, and bicyclic lactones are obtained in high yields and with excellent enantiomeric excesses. With the employment of γ-substituted allenoates as racemic precursors, a novel dynamic kinetic resolution of allenes via RC reaction is observed, which allows for facile synthesis of highly enantiomerically enriched allenes.
Rauhut-Currier（RC）反应是有机合成中构建碳-碳键的有效方法。然而，涉及丙二烯酸酯底物的 RC 反应非常罕见，特别是丙二烯酸酯的不对称分子内 RC 反应尚未被发现。在这里，我们表明在 1 mol%β-ICD 的存在下，分子内 RC 反应顺利进行，并且以高产率和优异的对映过量获得了双环内酯。使用γ-取代的丙二烯酸酯作为外消旋前体，通过 RC 反应观察到一种新的丙二烯的动态动力学拆分，这使得高对映体富集的丙二烯的简便合成成为可能。
