Reversible redox processes involving hydroquinones and quinones are ubiquitous in biological reaction networks, materials science, and catalysis. While extensively studied in intermolecular settings, less is known about intramolecular scenarios. Herein, we report hydroquinone–quinone hybrid molecules that form two‐stereocenter dihydrobenzofurans via intramolecular cyclization under thermodynamic control. A π‐methylhistidine peptide‐catalyzed kinetic resolution allowed us to study the stereodynamic behavior of enantio‐ and diastereo‐enriched dihydrofurans. In the course of this study, it was revealed that a reversible intramolecular redox‐interconversion network connects all four possible stereoisomers via inversion of a quaternary carbon stereocenter without achiral intermediates. As a result, these findings on hydroquinone‐quinone hybrid molecules provide insights into potential natural origin and synthetic access of the common dihydrobenzofuran motif.

中文翻译：

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对苯二酚-苯醌杂二氢苯并呋喃中的三级和四级碳立体中心的立体动力学氧化还原互变网络

涉及对苯二酚和醌的可逆氧化还原过程在生物反应网络，材料科学和催化中无处不在。尽管在分子间环境中进行了广泛的研究，但对分子内场景所知甚少。在本文中，我们报道了在热力学控制下通过分子内环化形成两个立体中心二氢苯并呋喃的氢醌-醌杂化分子。π-甲基组氨酸肽催化的动力学拆分使我们能够研究对映体和非对映体富集的二氢呋喃的立体动力学行为。在这项研究的过程中，揭示了一个可逆的分子内氧化还原-相互转化网络通过四价碳立体中心的转化而连接了所有四个可能的立体异构体，而没有非手性中间体。因此，