Chiral eight-membered heterocycles comprise a diverse array of natural products and bioactive compounds, yet accessing them poses significant challenges. Here we report a gold-catalyzed stereoselective (4 + 4) cycloaddition as a reliable and divergent strategy, enabling readily accessible precursors (anthranils and ortho-quinone methides) to be intercepted by in situ generated gold-furyl 1,4-dipoles, delivering previously inaccessible chiral furan/pyrrole-containing eight-membered heterocycles with good results (56 examples, all >20 : 1 dr, up to 99% ee). Moreover, we achieve a remarkably efficient kinetic resolution (KR) process (s factor up to 747). The scale-up synthesis and diversified transformations of cycloadducts highlight the synthetic potential of this protocol. Computational calculations provide an in-depth understanding of the stereoselective cycloaddition process.

中文翻译：

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通过金催化发散 (4 + 4) 环加成反应动力学拆分 1-(1-炔基)环丙基酮：立体选择性获得呋喃稠合八元杂环


手性八元杂环由多种天然产物和生物活性化合物组成，但获取它们面临着巨大的挑战。在这里，我们报告了金催化的立体选择性（4 + 4）环加成作为一种可靠且发散的策略，使易于获得的前体（邻氨基苯甲醚和邻醌甲基化物）能够被原位生成的金-呋喃基1,4-偶极子拦截，从而提供以前无法获得的含手性呋喃/吡咯的八元杂环，取得了良好的结果（56 个例子，全部 >20 : 1 dr，高达 99% ee）。此外，我们实现了非常高效的动力学拆分 (KR) 过程（s 因子高达 747）。环加合物的放大合成和多样化转化凸显了该方案的合成潜力。计算提供了对立体选择性环加成过程的深入理解。