Biomimetic catalytic aerobic oxidation of C–sp(3)–H bonds under mild conditions using galactose oxidase model compound CuIIL,Chemical Science

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Biomimetic catalytic aerobic oxidation of C–sp(3)–H bonds under mild conditions using galactose oxidase model compound CuIIL
Chemical Science ( IF 7.6 ) Pub Date : 2022-07-28 , DOI: 10.1039/d2sc02606f
Xiao-Hui Liu ₁ , Hai-Yang Yu ₁ , Jia-Ying Huang ₁ , Ji-Hu Su ₂ , Can Xue ₁ , Xian-Tai Zhou ₁ , Yao-Rong He ₃ , Qian He ₃ , De-Jing Xu ₁ , Chao Xiong ₃ , Hong-Bing Ji ₃

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Developing highly efficient catalytic protocols for C–sp(3)–H bond aerobic oxidation under mild conditions is a long-desired goal of chemists. Inspired by nature, a biomimetic approach for the aerobic oxidation of C–sp(3)–H by galactose oxidase model compound Cu^IIL and NHPI (N-hydroxyphthalimide) was developed. The Cu^IIL–NHPI system exhibited excellent performance in the oxidation of C–sp(3)–H bonds to ketones, especially for light alkanes. The biomimetic catalytic protocol had a broad substrate scope. Mechanistic studies revealed that the Cu^I-radical intermediate species generated from the intramolecular redox process of Cu^IILH₂ was critical for O₂ activation. Kinetic experiments showed that the activation of NHPI was the rate-determining step. Furthermore, activation of NHPI in the Cu^IIL–NHPI system was demonstrated by time-resolved EPR results. The persistent PINO (phthalimide-N-oxyl) radical mechanism for the aerobic oxidation of C–sp(3)–H bond was demonstrated.

中文翻译：

使用半乳糖氧化酶模型化合物 CuIIL 在温和条件下仿生催化有氧氧化 C–sp(3)–H 键

开发温和条件下C-sp(3)-H键有氧氧化的高效催化方案是化学家长期以来的目标。受大自然的启发，开发了一种通过半乳糖氧化酶模型化合物 Cu ^II L 和 NHPI（N-羟基邻苯二甲酰亚胺）对 C-sp(3)-H 有氧氧化的仿生方法。Cu ^II L-NHPI 体系在 C-sp(3)-H 键氧化成酮方面表现出优异的性能，特别是对于轻质烷烃。仿生催化方案具有广泛的底物范围。机理研究表明，Cu ^II LH _{2分子内氧化还原过程中产生的Cu}^I自由基中间体对于O ₂活化至关重要。动力学实验表明NHPI的激活是速率决定步骤。此外，时间分辨 EPR 结果证明了Cu ^{II L-NHPI 系统中 NHPI 的激活。}证明了 C-sp(3)-H 键有氧氧化的持久 PINO（邻苯二甲酰亚胺-N-氧基）自由基机制。

更新日期：2022-07-28

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