可见光催化二氧化碳参与多氟芳烃的选择性C-F键羧基化

doi:10.1016/S1872-2067(22)64140-8

催化学报 ›› 2022, Vol. 43 ›› Issue (9): 2388-2394.DOI: 10.1016/S1872-2067(22)64140-8

可见光催化二氧化碳参与多氟芳烃的选择性C-F键羧基化

伯知豫^†, 颜思顺^†, 高田宇, 宋磊, 冉川昆, 何轶, 章炜^*(), 曹光梅, 余达刚^#()

四川大学化学学院, 绿色化学与技术教育部重点实验室, 四川成都610064

收稿日期:2022-04-29 接受日期:2022-05-19 出版日期:2022-09-18 发布日期:2022-07-20
通讯作者: 章炜,余达刚
作者简介:第一联系人：
†共同第一作者.
基金资助:
国家自然科学基金(22101191);国家自然科学基金(21822108);中国博士后面上基金(2021M692261);四川省青年科技创新研究团队项目(20CXTD0112);中央引导地方科技发展资金项目(自由探索类基础研究项目, 2021ZYD0063(自由探索类基础研究项目);中央引导地方科技发展资金项目(自由探索类基础研究项目, 2021ZYD0063(2021ZYD0063);中央高校基本科研业务费专项资金资助

Visible-light photoredox-catalyzed selective carboxylation of C(sp²)-F bonds in polyfluoroarenes with CO₂

Zhi-Yu Bo^†, Si-Shun Yan^†, Tian-Yu Gao, Lei Song, Chuan-Kun Ran, Yi He, Wei Zhang^*(), Guang-Mei Cao, Da-Gang Yu^#()

Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, Sichuan, China

Received:2022-04-29 Accepted:2022-05-19 Online:2022-09-18 Published:2022-07-20
Contact: Wei Zhang, Da-Gang Yu
About author:First author contact:
†Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22101191);National Natural Science Foundation of China(21822108);China Postdoctoral Science Foundation(2021M692261);Central Government Funds of Guiding Local Scientific and Technological Development for Sichuan Province(2021ZYD0063);and the Fundamental Research Funds for the Central Universities

摘要/Abstract

摘要：

二氧化碳(CO₂)具有廉价易得、无毒、可循环再生等优点, 是合成化学中优良的碳一(C1)合成子, 可用于多种大宗化学品及精细化学品的合成. 然而, 由于CO₂具有较高的热力学稳定性及动力学惰性, 其在温和条件下选择性转化较为困难. 多氟芳基羧酸是一种重要的含氟砌块, 具有独特的物化性质及生理活性, 在医药、农药和有机光电材料等领域中均有广泛应用. 多氟化合物C-F键的选择性羧基化反应是构建含氟羧酸的重要手段之一. 然而, 由于C-F键具有较高的键解离能, 实现其选择性断裂及官能团化反应较为困难, 因此CO₂参与芳基C-F键的羧基化反应面临着极大的挑战. 目前, 该领域仅有少量关于电化学和过渡金属催化的报道, 且存在需使用牺牲阳极、当量的金属还原剂、额外引入导向基以及反应条件苛刻等问题, 因此, 需要发展其他策略实现温和条件下CO₂参与的芳基C-F键羧基化反应. 可见光是一种来源广泛、可再生的清洁能源. 可见光催化反应具有条件温和、官能团兼容性高和绿色环保等优点, 在近年来得到了较大的发展, 并为多种惰性底物以及惰性化学键的活化提供了新的手段.

本文利用可见光催化, 在温和条件下实现了CO₂参与多氟芳烃惰性C-F键的选择性羧基化反应, 合成了一系列重要的多氟芳基羧酸类产物. 该反应具有原料易得、条件温和、底物范围广、产率及区域选择性良好等优点. 一系列五氟、四氟以及三氟芳烃均能较好地参与反应, 各种吸电子、供电子取代基以及杂芳环取代基均能兼容于该反应体系中. 此外, 该策略也为一些含氟液晶分子提供了快速简洁的合成方法, 并可对一些天然产物衍生物以及含氟液晶分子进行后期修饰, 合成其他方法难以获得的多氟芳基羧酸产物. 与之前报道中直接捕获不稳定的多氟芳基自由基物种不同, 该反应可能经历了多氟芳基自由基还原为芳基碳负离子的过程. 综上, 本文丰富了多氟芳烃C-F键官能团化的方法, 并为可见光催化芳基C-F键的转化提供了新的催化模式, 具有较大的学术意义和较好的应用前景.

关键词: 二氧化碳, 可见光催化, 羧基化, C-F键官能团化, 多氟芳烃

Abstract:

Visible light-driven carboxylation with CO₂ have emerged as a sustainable and powerful way to transfer waste to treasure. However, it is still challenging for aryl fluorides due to the low reactivities of both C(sp²)-F bonds and CO₂. Herein, we report the first photocatalytic carboxylation of aryl C-F bonds with CO₂. The visible-light photoredox catalysis enables selective carboxylation of strong C(sp²)-F bonds in diverse polyfluoroarenes, such as penta-, tetra-, and tri-fluoroarenes under mild conditions, providing a facile access to a series of important polyfluoroaryl carboxylic acids with good yields. In contrast to previous reports of direct capture of polyfluoroaryl radicals, mechanistic studies suggest that the reduction of fleeting polyfluoroaryl radicals into polyfluoroaryl anions might be involved in this transformation, which may open a new avenue for photocatalytic functionalization of aryl C-F bonds.

Key words: Carbon dioxide, Visible-light photoredox catalysis, Carboxylation, C-F functionalization, Polyfluoroarenes

伯知豫, 颜思顺, 高田宇, 宋磊, 冉川昆, 何轶, 章炜, 曹光梅, 余达刚. 可见光催化二氧化碳参与多氟芳烃的选择性C-F键羧基化[J]. 催化学报, 2022, 43(9): 2388-2394.

Zhi-Yu Bo, Si-Shun Yan, Tian-Yu Gao, Lei Song, Chuan-Kun Ran, Yi He, Wei Zhang, Guang-Mei Cao, Da-Gang Yu. Visible-light photoredox-catalyzed selective carboxylation of C(sp²)-F bonds in polyfluoroarenes with CO₂[J]. Chinese Journal of Catalysis, 2022, 43(9): 2388-2394.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(22)64140-8

https://www.cjcatal.com/CN/Y2022/V43/I9/2388

图/表 8

Scheme 1. Visible-light photocatalytic carboxylation of aryl (pseudo)halides.

Fig. 1. Selected examples of polyfluoroaryl acids and derivatives.

Table 1 Optimization of reaction conditions.

Entry	Variations form the standard	Yield (%)
1	none	78
2	w/o [Ir(ppy)₂(dtbbpy)]PF₆	trace
3	w/o light	N.D.
4	N₂ instead of CO₂	trace
5	w/o HCO₂K	< 5
6	quinuclidine as HAT reagent	< 5
7	w/o DABCO	37
8	w/o base	44
9	DMSO instead of DMF	(43)
10	Cs₂CO₃ (2.5 eq.) instead of CsF/Cs₂CO₃	61
11	CsF (2.5 eq.) instead of CsF/Cs₂CO₃	62

Scheme 2. Substrate scopes of pentafluoroarenes. Reaction conditions as shown in Table 1, entry 1. Regioselectivity was detected by crude GC. “Others” refers to ortho and meta regioisomers. a 42 h. b HCO2K (2.5 eq.) was used. c CsF (2.5 eq.), Cs2CO3 (1.5 eq.) were used. 30 h. d 48 h. e Cs2CO3 (2.5 eq.) was used as sole base. DMF (2 mL) and DMSO (300 μL) were used as co-solvent. 34 h.

Scheme 3. Substrate scope of trifluoroarenes. Reaction conditions: 3 (0.2 mmol, 1 eq.), [Ir(ppy)2](dtbbpy)]PF6 (2.5 mol%), DABCO (60 mol%), HCO2K (2.5 eq.), Cs2CO3 (2.5 eq.), DMF (2 mL), DMSO (300 μL), irradiated by 30 W blue LEDs at room temperature under CO2 (1 atm) for 38 h. Isolated yields. Single regioisomer was detected. a 32 h. b HCO2K (3 eq.) was used. c DMSO (2 mL) was used as sole solvent. 24 h. d [Ir(ppy)2](dtbbpy)]PF6 (2 mol%), DABCO (50 mol%) and HCO2K (2 eq.) were used. 32 h. e HCO2K (3.5 eq.) was used.

Scheme 4. Substrate scope of tetrafluoroarenes. Reaction conditions as shown in Table 1, entry 1. Regioselectivity was detected by crude GC. a HCO2K (3 eq.) was used.

Scheme 5. Control experiments.

Scheme 6. Proposed mechanism.

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可见光催化二氧化碳参与多氟芳烃的选择性C-F键羧基化

Visible-light photoredox-catalyzed selective carboxylation of C(sp²)-F bonds in polyfluoroarenes with CO₂

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可见光催化二氧化碳参与多氟芳烃的选择性C-F键羧基化

Visible-light photoredox-catalyzed selective carboxylation of C(sp2)-F bonds in polyfluoroarenes with CO2

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Visible-light photoredox-catalyzed selective carboxylation of C(sp²)-F bonds in polyfluoroarenes with CO₂