Given the tremendous success of (p‐cymene)RuII‐catalyzed C−H activation over the past 20 years, the community has long been aware that the development of chiral η6‐benzene (Ben) ligands should be a potent strategy for achieving the attractive but incredibly underdeveloped ruthenium(II)‐catalyzed asymmetric C−H activation. However, it has rarely been achieved due to the severe difficulty in developing proper chiral Ben ligands. In particular, designing chiral Ben ligands by connecting a benzene fragment to a chiral framework including benzene rings remained an unsolved challenge until this effort. Here we present a novel class of axially chiral Ben ligands derived from readily available (S)‐5,5',6,6',7,7',8,8'‐octahydro‐1,1'‐bi‐2‐naphthol ((S)‐H8‐BINOL) in 4‐8 steps. Notably, when coordinated with ruthenium, such chiral Ben ligand containing three benzene rings only forms one of the three possible isomeric BenRuII complexes. The related chiral BenRuII catalysts could effectively catalyze the asymmetric C−H activation of N‐sulfonyl ketimines with alkynes, affording a range of chiral spirocyclic sultams in up to 99% yield with up to >99% ee. These catalysts are expected to find broad applications in future.

中文翻译：

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H8-BINOL 衍生的手性 η6-苯配体：钌催化不对称 C−H 活化的新机遇

鉴于过去 20 年来 (p-伞花烃)RuII 催化的 C−H 活化取得了巨大成功，业界早就意识到手性 η6-苯 (Ben) 配体的开发应该是实现有吸引力的有效策略。但令人难以置信的是，钌(II)催化的不对称C−H活化不发达。然而，由于开发合适的手性 Ben 配体非常困难，这一目标很少实现。特别是，通过将苯片段连接到包含苯环的手性框架来设计手性 Ben 配体，在这项工作之前仍然是一个尚未解决的挑战。在这里，我们提出了一类新型的轴向手性 Ben 配体，衍生自容易获得的 (S)-5,5',6,6',7,7',8,8'-八氢-1,1'-bi-2-萘酚 ((S)-H8-BINOL) 分 4-8 个步骤。值得注意的是，当与钌配位时，这种含有三个苯环的手性Ben配体仅形成三种可能的异构BenRuII配合物之一。相关的手性BenRuII催化剂可以有效地催化N-磺酰酮亚胺与炔烃的不对称C-H活化，得到一系列手性螺环磺内酰胺，产率高达99%，ee高达99%以上。这些催化剂有望在未来得到广泛的应用。