Catalytic Asymmetric C–H Activation/Cyclization of Sulfoximines with Sulfoxonium Ylides by a Chiral η6-Benzene Ruthenium(II) Catalyst

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL ACS Catalysis Pub Date : 2024-11-12 DOI:10.1021/acscatal.4c04798

Huan Liu, Ji-Jun Jiang, Jun Wang

引用次数: 0

Abstract

Chiral η⁶-benzene ruthenium(II) (BenRu^II)-catalyzed asymmetric C–H activations are challenging and rarely seen in the literature. Herein, the asymmetric C–H activation/cyclization of sulfoximines with sulfoxonium ylides catalyzed by the chiral BenRu^II catalyst derived from (S)-H₈–BINOL is described. It provides efficient access to various sulfur-chiral 1,2-benzothiazine 1-oxides in high yields with high enantioselectivities (up to 99% yield and 98% ee). Kinetic resolution of racemic sulfoximines was also feasible. The reaction mechanism was studied by the tool of H/D exchange and the kinetic isotope effect. The metallacycle revealing the origin of chiral induction was prepared, characterized, and proved effective for the model reaction. This work demonstrates the great potential of chiral BenRu^II catalysts for asymmetric C–H activation.

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手性 η6-苯钌（II）催化剂催化磺酰亚胺与磺酰亚胺的不对称 C-H 活化/环化反应

手性η6-苯钌（II）（BenRuII）催化的不对称 C-H 活化具有挑战性，在文献中很少见。本文介绍了由 (S)-H8-BINOL 衍生的手性 BenRuII 催化剂催化的磺酰亚胺与磺酰亚胺的不对称 C-H 活化/环化。该催化剂能以高产率和高对映选择性（高达 99% 的产率和 98% 的ee）高效地获得各种硫手性 1,2-苯并噻嗪 1-氧化物。外消旋亚磺酰亚胺的动力学解析也是可行的。利用 H/D 交换工具和动力学同位素效应对反应机理进行了研究。制备了揭示手性诱导起源的金属环，对其进行了表征，并证明其对模型反应有效。这项工作证明了手性 BenRuII 催化剂在不对称 C-H 活化方面的巨大潜力。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.