An efficient catalytic asymmetric dearomatizing amination of 2-naphthols and phenols catalyzed by N,N′-dioxide-copper(I) complex as a chiral catalyst was presented. A variety of optically active β-naphthalenone compounds with a nitrogen-containing quaternary carbon stereocenter were obtained with high yield and enantioselectivity under mild reaction conditions. Mechanistic studies indicated that this Csp²–N dearomatizing coupling proceeds via 1,3-reductive elimination of phenolate-Cu^III-amino intermediate in five-membered ring transition states. The origin of enantioselectivity has also been elucidated based on density functional theory calculations.

提出了一种以 N,N'-二氧化铜 (I) 配合物作为手性催化剂催化 2-萘酚和苯酚的高效催化不对称脱芳构胺化反应。在温和的反应条件下，以高收率和对映选择性获得了多种具有含氮季碳立构中心的光学活性β-萘酮化合物。机理研究表明，这种 Csp ² -N 脱芳构化偶联是通过五元环过渡态中酚盐-Cu ^III -氨基中间体的 1,3-还原消除进行的。基于密度泛函理论计算也阐明了对映选择性的起源。