通过 Rh(II)催化的吗啉和α-重氮-β-酮酯的[3 + 6 + 3 + 6]缩合反应一步合成二氮杂大环。
One-Step Synthesis of Diaza Macrocycles by Rh(II)-Catalyzed [3 + 6 + 3 + 6] Condensations of Morpholines and α-Diazo-β-ketoesters.
机构信息
Department of Organic Chemistry , University of Geneva , Quai Ernest Ansermet 30 , 1211 Geneva 4 , Switzerland.
Laboratory of Crystallography , University of Geneva , Quai Ernest Ansermet 24 , 1211 Geneva 4 , Switzerland.
出版信息
Org Lett. 2019 Feb 1;21(3):687-691. doi: 10.1021/acs.orglett.8b03875. Epub 2019 Jan 18.
Selective formation of oxonium ylides from morpholines and α-diazo-β-ketoesters was achieved. This was applied to the high-concentration (0.5 M) dirhodium-catalyzed (0.1 mol %) [3 + 6 + 3 + 6] synthesis of 18-membered ring diaza macrocycles (46%-72%). Late-stage functionalization of these derivatives is demonstrated. Mechanistic evidence for a novel (undesired) diazo decomposition pathway is also reported.
通过 morpholines 和 α-重氮-β-酮酯，实现了氧鎓叶立德的选择性形成。这一方法被应用于高浓度（0.5 M）的二铑催化（0.1 mol%）的[3 + 6 + 3 + 6]合成 18 元环的二氮杂大环（46%-72%）。这些衍生物的后期功能化也得到了证明。同时也报道了一种新型（不希望的）重氮分解途径的机制证据。
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