Catalytic dearomatization of arenols is an uphill task that can serve as a powerful method to construct C‐C bonds with unsaturated coupling partners. Herein, a simple and efficient strategy for coupling naphthols with allylic alcohols is reported. A single Ru(II) pincer catalyzed coupling of naphthols with primary allylic alcohols led to the formation of benzo(f)chromanes, whereas the use of secondary alcohols delivered the hydroxyalkyl naphthols. Broad substrate scope and good functional group tolerance are demonstrated. Notably, a high diastereoselectivity is attained on chromanes. Hydroxyalkyl naphthols are synthetically transformed into spiroethers, and dearomative bromination is achieved on chromanes. Mechanistic studies revealed the involvement of tandem reactions, a formal O‐H bond activation of allylic alcohols by an active catalyst via amine‐amide metal‐ligand cooperation provided α‐β, unsaturated carbonyl intermediates, which further underwent 1,4 conjugate addition with dearomatized naphthols. One of the crucial intermediates, naphthyl radical, is elucidated by EPR studies and trapped using a radical scavenger. Liberated hydrogen and water molecules are the only byproducts in these transformations.

中文翻译：

---

官能化苯并[f]色烷和羟基烷基萘酚的合成：萘酚和烯丙基醇的催化偶联


芳烃的催化脱芳烃化是一项艰巨的任务，可以作为与不饱和偶联伴侣构建 C-C 键的有力方法。在此，报道了一种简单而有效的萘酚与烯丙基醇偶联的策略。萘酚与伯烯丙基醇的单个 Ru（II） 钳催化偶联导致苯并 （f） 色氨酸的形成，而使用仲醇则产生羟基烷基萘酚。证明了广泛的底物范围和良好的官能团耐受性。值得注意的是，在色质上获得了高非对映选择性。羟基烷基萘酚合成转化为螺醚，并在色质上实现脱溴化。机理研究揭示了串联反应的参与，活性催化剂通过胺-酰胺金属-配体合作对烯丙基醇进行正式的 O-H 键活化，提供了 α-β，不饱和羰基中间体，进一步与脱芳烃萘酚进行 1,4 共轭加成。其中一种关键中间体，萘自由基，通过 EPR 研究阐明，并使用自由基清除剂捕获。释放的氢和水分子是这些转化中唯一的副产品。