氯自由基介导的光催化芳基醚C(sp3)-H氧化生成酯

doi:10.1016/S1872-2067(23)64615-7

催化学报 ›› 2024, Vol. 58: 123-128.DOI: 10.1016/S1872-2067(23)64615-7

氯自由基介导的光催化芳基醚C(sp³)-H氧化生成酯

刘玉庭^a^,^b, 聂贝黎^b^,^c, 李宁^b, 刘慧芳^b,*(), 王峰^a^,^b^,^d,*()

^a中国科学技术大学化学物理系, 安徽合肥230026
^b中国科学院大连化学物理研究所, 辽宁大连116023
^c郑州大学河南先进技术研究院, 河南郑州450003
^d中国科学院大学, 北京100049

收稿日期:2023-12-13 接受日期:2024-01-26 出版日期:2024-03-18 发布日期:2024-03-28
通讯作者: *电子信箱: liuhuifang@dicp.ac.cn (刘慧芳),wangfeng@dicp.ac.cn (王峰).
基金资助:
国家重点研发计划(2022YFA1504904);国家自然科学基金(22272169);国家自然科学基金(22025206);国家自然科学基金(32130073);国家自然科学基金(22172163);大连市高层次人才创新支持计划(2022RG13)

Chlorine radical-mediated photocatalytic C(sp³)-H bond oxidation of aryl ethers to esters

Yuting Liu^a^,^b, Beili Nie^b^,^c, Ning Li^b, Huifang Liu^b,*(), Feng Wang^a^,^b^,^d,*()

^aDepartment of Chemical Physics, University of Science and Technology of China, Hefei 230026, Anhui, China
^bDalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^cHenan Institute of Advanced Technology, Zhengzhou University, Zhengzhou 450003, Henan, China
^dUniversity of Chinese Academy of Sciences, Beijing 100049, China

Received:2023-12-13 Accepted:2024-01-26 Online:2024-03-18 Published:2024-03-28
Contact: *E-mail: liuhuifang@dicp.ac.cn (H. Liu),wangfeng@dicp.ac.cn (F. Wang).
Supported by:
National Key R&D Program of China(2022YFA1504904);National Natural Science Foundation of China(22272169);National Natural Science Foundation of China(22025206);National Natural Science Foundation of China(32130073);National Natural Science Foundation of China(22172163);Dalian Innovation Support Plan for High Level Talents(2022RG13)

摘要/Abstract

摘要：

饱和的碳氢键氧化是合成化学和化学工业中一类重要的化学反应. 然而, 饱和C(sp³)-H键离解能(BDEs)较高、极性较弱, 导致了底物难以活化和催化转化效率较低等问题. 在过去的几十年, C(sp³)-H键的定向活化转化取得了重要的进展. 其中, 关于C(sp³)-H键催化氧化的研究主要涉及一些键能低的、预活化的C-H键, 包括苄基型、亚甲基型、脂肪族X-CH₂ (X = O, N)和甲苯等, 含有未活化C(sp³)-H键的复杂化合物的选择性氧化仍具有挑战性. 例如, 芳基醚C(sp³)-H键功能化通常采用计量的过氧化物氧化剂, 或者通过单电子氧化和碱促进的去质子化进一步构建C-C/C-N键, 产物选择性较低, 也带来了一些不利的环境影响. 因此, 有必要开发高效、温和的芳基醚C(sp³)-H键选择氧化方法, 并将其应用于有机合成和药物开发.

近年来, 光催化C(sp³)-H键氧化因其操作简便、氧化还原中性等优点, 已发展成为一种有用且多样的催化研究工具. 本文发展了一种利用氧气作为氧化剂, 在可见光驱动下选择性地将芳基醚C(sp³)-H键氧化成为甲酸苯酯类产物的新方法. 使用Mes-10-phenyl- Acr⁺-BF₄^-光催化剂, 高效活化多种氯源(如盐酸、无机氯盐和有机氯化物)得到氯自由基, 由于其具有较高的氧化能力(+2.03 V vs. SCE)和对氢原子的亲和力, 能够通过氢原子转移过程活化芳基醚C(sp³)-键, 攫取氢自由基得到相应的烷基碳自由基(•CH₂OPh)中间体, 进一步被分子氧选择氧化得到酯类目标产物. 研究结果表明, 多种链状芳基醚和不同取代(如给电子基和吸电子基)芳基醚均可发生氧化反应, 高收率地合成了一系列官能团丰富的甲酸苯酯类化合物. 本文方法具有反应条件温和、操作简单、官能团耐受性好以及可规模化放大等优点, 并且少量的水对反应没有明显影响. 机理实验研究结果表明, 芳基醚C(sp³)-H键的断裂是反应过程的决速步骤. 紫外可见吸收光谱结果表明, 氯离子与催化剂之间的相互作用强于底物, 并且自由基捕获实验证实反应体系中存在氯自由基和烷基碳自由基物种, 表明反应经历自由基路径. 此外, 电子顺磁共振测试结果表明, 反应过程中存在单线态氧物种, 可能是激发态的光催化剂直接与氧气发生能量转移得到; 同位素实验(¹⁸O)揭示了甲酸苯酯类化合物氧的来源.

综上, 本文实现了温和条件下光催化芳基醚C(sp³)-H键选择氧化反应, 高收率合成了一系列甲酸苯酯类化合物. 该方法避免了化学计量的过氧化物和碱等添加剂的使用以及底物的过度氧化, 阐明了催化反应机制, 为其他醚类化合物的C(sp³)-H键氧化功能化提供了新思路, 为后续化学合成和药物开发提供了参考和启示.

关键词: 氯自由基, 光催化, C(sp³)-H键, 催化氧化, 芳基醚

Abstract:

The C(sp³)-H functionalization of naturally abundant alkanes is of great importance, whereas C-H bond oxidation of aryl ethers in a redox-neutral and environmental-friendly manner remains a challenge. Herein, we report a novel method of visible-light-driven C(sp³)-H bond oxidation of aryl ethers selectively into ester products using oxygen as the oxidant. During the photocatalytic reaction using Mes-10-phenyl-Acr⁺-BF₄^- catalyst, chlorine radicals are generated from a wide variety of chloride sources and can effectively activate aryl ether C(sp³)-H bonds into alkyl radicals through the hydrogen atom transfer process. Aryl ethers with different substituents can be oxidized to esters in good to excellent yields. This work presents a new photocatalytic strategy for C(sp³)-H oxidation of aryl ethers in a convenient and green manner.

Key words: Chlorine radical, Photocatalysis, C(sp³)-H bond, Catalytic oxidation, Aryl ethers

刘玉庭, 聂贝黎, 李宁, 刘慧芳, 王峰. 氯自由基介导的光催化芳基醚C(sp³)-H氧化生成酯[J]. 催化学报, 2024, 58: 123-128.

Yuting Liu, Beili Nie, Ning Li, Huifang Liu, Feng Wang. Chlorine radical-mediated photocatalytic C(sp³)-H bond oxidation of aryl ethers to esters[J]. Chinese Journal of Catalysis, 2024, 58: 123-128.

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图/表 7

Scheme 1. Strategies for C(sp3)-H bond functionalization.

Fig. 1. Photocatalytic C(sp3)-H bond oxidation of anisole under different conditions. (a) Effects of different solvents. (b) H+ cation detection in the CH2Cl2, MeCN and CH2Cl2 + MeCN (v/v = 1: 1) mixed solvents after reaction for 0.5 h. (c) Optimizations using various chloride additives. Reaction conditions: anisole (0.1 mmol), PC-Mes (2.5 mol%), [Cl] (20 mol%), 455 nm LEDs, solvent (1.0 mL), 0.2 MPa of O2, 3 h. PC-Mes = Mes-10-phenyl-Acr+-BF4-.

Fig. 2. (A) Kinetic profile. (B) Control experiments. Standard conditions: anisole (0.1 mmol), PC-Mes (2.5 mol%) and LiCl (20 mol%) were irradiated using 455 nm LEDs in MeCN (1.0 mL) for 3 h under 0.2 MPa of O2.

Fig. 3. Mechanistic investigations. Standard conditions: substrate (0.1 mmol), PC-Mes (2.5 mol%) and LiCl (20 mol%) were irradiated using 455 nm LEDs in MeCN (1.0 mL) under 0.2 MPa of O2.

Scheme 2. Proposed mechanism for C(sp3)-H bond oxidation of aryl ethers by chlorine radical.

Scheme 3. Scope of photocatalytic C(sp3)-H bond oxidation of aryl ethers. a Reaction conditions: substrate 1a?1p, 1q (0.1 mmol), PC-Mes (2.5 mol%) and LiCl (20 mol%) were irradiated using 455 nm LEDs in MeCN (1.0 mL) for 5 h under 0.2 MPa of O2. b The yield of 2a in parentheses. c Run for 2 h. d Run for 12 h. e Run for 3 h. f Run for 0.3 h. The yield of chroman-2-one (2g’) were determined by 1H-NMR in parentheses. g Run for 8 h. h Run for 4 h. i Run for 10 h. j Run for 6 h.

Scheme 4. Gram-scale reaction for C(sp3)-H bond oxidation of anisole.

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氯自由基介导的光催化芳基醚C(sp³)-H氧化生成酯

Chlorine radical-mediated photocatalytic C(sp³)-H bond oxidation of aryl ethers to esters

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