Vishe Mahesh, Hrdina Radim, Poblador-Bahamonde Amalia I, Besnard Céline, Guénée Laure, Bürgi Thomas, Lacour Jérôme
Department of Organic Chemistry , University of Geneva , Quai Ernest Ansermet 30 , CH-1211 Geneva 4 , Switzerland . Email:
Laboratory of Crystallography , University of Geneva , Quai Ernest Ansermet 24 , CH-1211 Geneva 4 , Switzerland.
Chem Sci. 2015 Aug 1;6(8):4923-4928. doi: 10.1039/c5sc01118c. Epub 2015 May 25.
The thermodynamically disfavored isomerization of α,β-unsaturated esters to deconjugated β,γ-unsaturated analogues occurs readily when coupled to an amidation. Within the framework of macrocyclic derivatives, it is shown that 15, 16, and 18 membered macrocycles react with BuOK and anilines to generate, in one-pot, β,γ-unsaturated amides (yields up to 88%). Importantly, single (chiral) diastereomers are isolated (d.r. > 49 : 1, H NMR) irrespective of the size and nature of the rings, showing an effective transmission of remote stereochemistry during the isomerization process. CSP-chromatographic resolution and absolute configuration determination by VCD are achieved.
当与酰胺化反应偶联时，α,β-不饱和酯向去共轭β,γ-不饱和类似物的热力学不利异构化反应很容易发生。在大环衍生物的框架内，研究表明，15元、16元和18元大环与叔丁醇钾和苯胺反应，可一锅法生成β,γ-不饱和酰胺（产率高达88%）。重要的是，无论环的大小和性质如何，都能分离出单一（手性）非对映异构体（核磁共振氢谱中，非对映体比例大于49:1），这表明在异构化过程中远程立体化学能够有效传递。通过手性固定相色谱实现了拆分，并通过振动圆二色光谱确定了绝对构型。
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