可见光催化二氧化碳与苄位卤代物的羧基化: 温和条件且无过渡金属

doi:10.1016/S1872-2067(21)63859-7

催化学报 ›› 2022, Vol. 43 ›› Issue (7): 1667-1673.DOI: 10.1016/S1872-2067(21)63859-7

• 二氧化碳催化转化专栏 • 上一篇下一篇

可见光催化二氧化碳与苄位卤代物的羧基化: 温和条件且无过渡金属

敬科^a, 魏明恺^a, 颜思顺^a, 廖黎丽^a, 牛亚楠^a, 罗书平^b, 于博^a^,^*(), 余达刚^a^,^#()

^a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
^b浙江工业大学, 绿色化学合成技术国家重点实验室(筹), 浙江杭州310014

收稿日期:2021-04-13 接受日期:2021-05-22 出版日期:2022-07-18 发布日期:2021-06-15
通讯作者: 于博,余达刚
基金资助:
国家自然科学基金(21822108);国家自然科学基金(21772129);中国博士后面上基金(2020M683301);四川省青年科技创新研究团队项目(20CXTD0112)

Visible-light photoredox-catalyzed carboxylation of benzyl halides with CO₂: Mild and transition-metal-free

Ke Jing^a, Ming-Kai Wei^a, Si-Shun Yan^a, Li-Li Liao^a, Ya-Nan Niu^a, Shu-Ping Luo^b, Bo Yu^a^,^*(), Da-Gang Yu^a^,^#()

^aKey Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, Sichuan, China
^bState Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China

Received:2021-04-13 Accepted:2021-05-22 Online:2022-07-18 Published:2021-06-15
Contact: Bo Yu, Da-Gang Yu
About author:Da-Gang Yu (College of Chemistry, Sichuan University) was invited as a young member of the 6^th Editorial Board of Chin. J Catal. in 2020. Prof. Da-Gang Yu received his B.S. degree from Sichuan University (P. R. China) in 2007 and Ph.D. degree with Prof. Zhang-Jie Shi from Peking University (P. R. China), 2012. He carried out postdoctoral research with Humboldt fellowship in the group of Prof. Frank Glorius, Muenster University (Germany). Since 2015, he has been working independently in Sichuan University (China) with support from “The Thousand Young Talents Plan” and the National Natural Science Foundation of China‒Outstanding Young Scholars. His research interests mainly focus on novel transformations of CO₂, radical chemistry and novel transition-metal catalysis. He has coauthored about 90 peer-reviewed papers and 11 patents.
Supported by:
National Natural Science Foundation of China(21822108);National Natural Science Foundation of China(21772129);China Postdoctoral Science Foundation(2020M683301);Sichuan Science and Technology Program(20CXTD0112)

摘要/Abstract

摘要：

二氧化碳(CO₂)作为一种无毒、廉价、可再生的碳一合成子, 被广泛用于合成重要的精细化学品. 芳基乙酸广泛存在于许多药物分子中, 是一类重要的羧酸分子. 苄位卤代物具有商业可得且价格低廉的优势, 是合成芳基乙酸的理想底物. 因此, 以苄位卤代物和CO₂为原料合成芳基乙酸具有很大的吸引力. 传统的合成方法需要将苄基卤化物预先制备成水、氧敏感的苄位金属试剂, 再与CO₂发生羧基化反应, 但因兼容性较差, 操作繁琐, 限制了实际应用. 另外, 苄位卤化物与CO₂的直接电羧基化反应也有报道, 但存在需要牺牲阳极、使用贵金属电极和支持电解质等不足. 此外, 过渡金属催化苄位卤代物与CO₂羧基化反应得到长足发展, 但也存在底物范围有限、官能团兼容性不佳、使用金属还原剂和存在重金属污染等问题.

近年来, 可见光催化已经成为实现CO₂高效转化的有力工具, 具有绿色环保、官能团兼容性好等特点. 如果能利用可见光催化实现苄位卤代物与CO₂的还原羧基化, 将可以进一步提升该类转化的底物适用性和反应的实用性. 本文利用廉价的有机染料为光敏剂和有机胺为电子给体, 在常压CO₂和室温条件下, 实现了苄位氯代物和溴代物的还原羧基化反应. 一级、二级和三级的苄位卤代物都能顺利地参与该羧基化反应, 芳环上的卤原子和硼酸酯等常见的偶联官能团也能兼容. 另外, 成功地将这种方法放大到了克级反应, 合成了一些重要的药物分子和药物分子前体, 实现了一些重要的天然产物的羧酸化衍生, 证明了这种合成方法具有潜在的应用价值. 机理实验结果表明, 该反应很可能主要经历还原态的光敏剂对苄位卤代物的两次单电子还原过程, 从而先后产生苄位自由基和苄位碳负离子, 后者可以快速捕获CO₂生成羧酸盐, 质子化后生成芳基乙酸. 综上, 可见光催化的羧基化反应具有反应条件温和、无需过渡金属参与、底物范围广、官能团兼容性好、易克级放大、催化剂用量低等优势, 为实现芳基乙酸的高效合成提供了一种新方法.

关键词: 二氧化碳, 可见光催化, 羧基化, 芳基乙酸, 苄位卤代物

Abstract:

The visible-light photoredox-catalyzed carboxylation of benzyl chlorides and bromides with CO₂ has been reported. With inexpensive organic dyes as photocatalysts and amines as electron donors, this carboxylation proceeds well in the absence of sensitive organometallic reagents, transition metal catalysts, or metallic reductants. A wide range of commercially available and inexpensive benzyl halides undergo such carboxylation to give valuable aryl acetic acids, including several pharmaceutical molecules and drug precursors, in moderate to high yields. Moreover, this reaction features mild reaction conditions (one atmospheric pressure of CO₂ and room temperature), broad substrate scope, good functional group tolerance, easy scalability, and low catalyst loading, thus providing an efficient approach for the assembly of aryl acetic acids.

Key words: Carbon dioxide, Visible-light photoredox catalysis, Carboxylation, Aryl acetic acids, Benzyl halides

敬科, 魏明恺, 颜思顺, 廖黎丽, 牛亚楠, 罗书平, 于博, 余达刚. 可见光催化二氧化碳与苄位卤代物的羧基化: 温和条件且无过渡金属[J]. 催化学报, 2022, 43(7): 1667-1673.

Ke Jing, Ming-Kai Wei, Si-Shun Yan, Li-Li Liao, Ya-Nan Niu, Shu-Ping Luo, Bo Yu, Da-Gang Yu. Visible-light photoredox-catalyzed carboxylation of benzyl halides with CO₂: Mild and transition-metal-free[J]. Chinese Journal of Catalysis, 2022, 43(7): 1667-1673.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63859-7

https://www.cjcatal.com/CN/Y2022/V43/I7/1667

图/表 10

Fig. 1. Representative aryl acetic acids.

Scheme 1. Reductive carboxylation of benzyl halides with CO2.

Table 1 Optimization of reaction conditions.

Scheme 2. Substrate scope of benzyl chlorides. Reaction conditions as presented in Table 1, entry 1. a 16 h. b 3 mol% 4CzIPN, 2.0 equiv. TMEDA, 2.0 equiv. Cs2CO3. c 2 mol% 4CzIPN. d The ratio of 2h to phenylacetic acid is 14.3:1. e 3 mol% 4DPAIPN, 24 h. f The ratio of 2q to phenylacetic acid is 16.7:1. g 5 h. h 6 h, then MeI (3 equiv.), 65 °C, 3 h. i 5 mL N,N-dimethylacetamide (DMAc) used instead of DMF. j 3 equiv. TMEDA. k 10 h. l 2 h. m 0.5 mol% 4DPAIPN.

Scheme 3. Substrate scope of benzyl bromides. Reaction conditions: 3 (0.2 mmol), 1 atm CO2, 4DPAIPN (0.002 mmol), TMEDA (0.12 mmol), Cs2CO3 (0.4 mmol), DMF (2 mL), 30 W blue LED, rt, 8 h. a 16 h. b Reaction conditions as shown in Table 1, entry 1.

Scheme 4. Reaction of allyl chloride 5. Reaction conditions as presented in Table 1, entry 1. The yield and ratio were determined by crude 1H NMR.

Scheme 5. Control experiments to confirm benzylic radical and benzylic anion intermediates.

Fig. 2. Reaction profiles of compounds 1a and 11. Reaction conditions for 1a as presented in Table 1, entry 1. Reaction conditions for 11: 11 (0.2 mmol), other conditions as presented in Table 1, entry 1 except the addition of TMEDA.

Fig. 3. Stern-Volmer luminescence studies.

Scheme 6. Plausible mechanisms.

参考文献

[1]	K. Huang, C.-L. Sun, Z.-J. Shi, Chem. Soc. Rev., 2011, 40, 2435-2452.
[2]	M. He, Y. Sun, B. Han, Angew. Chem. Int. Ed., 2013, 52, 9620-9633.
[3]	Q. Liu, L. P. Wu, R. Jackstell, M. Beller, Nat. Commun., 2015, 6, 5933.
[4]	Y. Li, X. Cui, K. Dong, K. Junge, M. Beller, ACS Catal., 2017, 7, 1077-1086.
[5]	A. Tortajada, J. Francisco, M. Börjesson, T. Moragas, R. Martin, Angew. Chem. Int. Ed., 2018, 57, 15948-15982.
[6]	Y. Cao, X. He, N. Wang, H.-R. Li, L.-N. He, Chin. J. Chem., 2018, 36, 644-659.
[7]	C. S. Yeung, Angew. Chem. Int. Ed., 2019, 58, 5492-5502.
[8]	Z. Zhang, L. Gong, X.-Y. Zhou, S.-S. Yan, J. Li, D.-G. Yu, Acta Chim. Sin., 2019, 77, 783-793.
[9]	Z. Zhang, J.-H. Ye, T. Ju, L.-L. Liao, H. Huang, Y.-Y. Gui, W.-J. Zhou, D.-G. Yu, ACS Catal., 2020, 10, 10871-10885.
[10]	Z. Fan, Z. Zhang, C. Xi, ChemSusChem, 2020, 13, 6201-6218.
[11]	C.-K. Ran, X.-W. Chen, Y.-Y. Gui, J. Liu, L. Song, K. Ren, D.-G. Yu, Sci. China Chem., 2020, 63, 1336-1351.
[12]	X. Guo, Y. Wang, J. Chen, G. Li, J.-B. Xia, Chin. J. Org. Chem., 2020, 40, 2208-2220.
[13]	X. He, L.-Q. Qiu, W.-J. Wang, K.-H. Chen, L.-N. He, Green Chem., 2020, 22, 7301-7320.
[14]	C. Zhou, M. Li, J. T. Yu, S. Sun, J. Cheng, Chin. J. Org. Chem., 2020, 40, 2221-2231.
[15]	L. Song, Y.-X. Jiang, Z. Zhang, Y.-Y. Gui, X.-Y. Zhou, D.-G. Yu, Chem. Commun., 2020, 56, 8355-8367.
[16]	S. Pradhan, S. Roy, B. Sahoo, I. Chatterjee, Chem. Eur. J., 2021, 27, 2254-2269.
[17]	B. Cai, H. W. Cheo, T. Liu, J. Wu, Angew. Chem. Int. Ed., 2021, 60, 18950-18980.
[18]	G. Zhang, Y. Cheng, M. Beller, F. Chen, Adv. Synth. Catal., 2021, 363, 1583-1596.
[19]	J.-H. Ye, T. Ju, H. Huang, L.-L. Liao, D.-G. Yu, Acc. Chem. Res., 2021, 54, 2518.
[20]	B. M. Bhanage, M. Arai, S. I. Fujita, Transformation and Utilization of Carbon Dioxide, Springer-Verlag, Berlin Heidelberg, 2014, 245-262.
[21]	D. Kong, P. J. Moon, E. K. J. Lui, O. Bsharat, R. J. Lundgren, Science, 2020, 369, 557-561.
[22]	C. E. I. Knappke, S. Grupe, D. Gärtner, M. Corpet, C. Gosmini, A. Jacobi von Wangelin, Chem. Eur. J., 2014, 20, 6828-6842.
[23]	H. Senboku, A. Katayama, Curr. Opin. Green Sustainable Chem., 2017, 3, 50-54.
[24]	G. Silvestri, S. Gambino, G. Filardo, A. Gulotta, Angew. Chem. Int. Ed., 1984, 23, 979-980.
[25]	A. A. Isse, A. Gennaro, Chem. Commun., 2002, 2798-2799.
[26]	T. Fujihara, K. Nogi, T. Xu, J. Terao, Y. Tsuji, J. Am. Chem. Soc., 2012, 134, 9106-9109.
[27]	T. León, A. Correa, R. Martin, J. Am. Chem. Soc., 2013, 135, 1221-1224.
[28]	A. Correa, T. León, R. Martin, J. Am. Chem. Soc., 2014, 136, 1062-1069.
[29]	T. Moragas, M. Gaydou, R. Martin, Angew. Chem. Int. Ed., 2016, 55, 5053-5057.
[30]	F. Juliá-Hernández, T. Moragas, J. Cornella, R. Martin, Nature, 2017, 545, 84-88.
[31]	Y.-G. Chen, B. Shuai, C. Ma, X.-J. Zhang, P. Fang, T.-S. Mei, Org. Lett., 2017, 19, 2969-2972.
[32]	Q.-Y. Meng, S. Wang, B. König, Angew. Chem. Int. Ed., 2017, 56, 13426-13430.
[33]	C. Ma, C.-Q. Zhao, X.-T. Xu, Z.-M. Li, X.-Y. Wang, K. Zhang, T.-S. Mei, Org. Lett., 2019, 21, 2464-2467.
[34]	B. Sahoo, P. Bellotti, F. Julia-Hernandez, Q.-Y. Meng, S. Crespi, B. König, R. Martin, Chem. Eur. J., 2019, 25, 9001-9005.
[35]	R. J. Somerville, C. Odena, M. F. Obst, N. Hazari, K. H. Hopmann, R. Martin, J. Am. Chem. Soc., 2020, 142, 10936-10941.
[36]	A. Correa, R. Martín, J. Am. Chem. Soc., 2009, 131, 15974-15975.
[37]	T. Mita, Y. Higuchi, Y. Sato, Chem. Eur. J., 2015, 21, 16391-16394.
[38]	S. Zhang, W.-Q. Chen, A. Yu, L.-N. He, ChemCatChem, 2015, 7, 3972-3977.
[39]	K. Shimomaki, K. Murata, R. Martin, N. Iwasawa, J. Am. Chem. Soc., 2017, 139, 9467-9470.
[40]	K. Shimomaki, T. Nakajima, J. Caner, N. Toriumi, N. Iwasawa, Org. Lett., 2019, 21, 4486-4489.
[41]	S. K. Bhunia, P. Das, S. Nandi, R. Jana, Org. Lett., 2019, 21, 4632-4637.
[42]	C. Zhu, Y.-F. Zhang, Z.-Y. Liu, L. Zhou, H. Liu, C. Feng, Chem. Sci., 2019, 10, 6721-6726.
[43]	H. Tran-Vu, O. Daugulis, ACS Catal., 2013, 3, 2417-2420.
[44]	S.-S. Yan, D.-S. Wu, J.-H. Ye, L. Gong, X. Zeng, C.-K. Ran, Y.-Y. Gui, J. Li, D.-G. Yu, ACS Catal., 2019, 9, 6987-6992.
[45]	S.-L. Xie, X.-Y. Cui, X.-T. Gao, F. Zhou, H.-H. Wu, J. Zhou, Org. Chem. Front., 2019, 6, 3678-3682.
[46]	K. Nogi, T. Fujihara, J. Terao, Y. Tsuji, Chem. Commun., 2014, 50, 13052-13055.
[47]	J. Xuan, W.-J. Xiao, Angew. Chem. Int. Ed., 2012, 51, 6828-6838.
[48]	C. K. Prier, D. A. Rankic, D. W. C. MacMillan, Chem. Rev., 2013, 113, 5322-5363.
[49]	D. M. Schultz, T. P. Yoon, Science, 2014, 343, 1239176.
[50]	N. A. Romero, D. A. Nicewicz, Chem. Rev., 2016, 116, 10075-10166.
[51]	Q.-Q. Zhou, Y.-Q. Zou, L.-Q. Lu, W.-J. Xiao, Angew. Chem. Int. Ed., 2019, 58, 1586-1604.
[52]	Y. Chen, L.-Q. Lu, D.-G. Yu, C.-J. Zhu, W.-J. Xiao, Sci. China Chem., 2019, 62, 24-57.
[53]	L. Buzzetti, G. E. M. Crisenza, P. Melchiorre, Angew. Chem. Int. Ed., 2019, 58, 3730-3747.
[54]	X. Ren, Z. Lu, Chin. J. Catal., 2019, 40, 1003-1019.
[55]	K. Murata, N. Numasawa, K. Shimomaki, J. Takaya, N. Iwasawa, Chem. Commun., 2017, 53, 3098-3101.
[56]	V. R. Yatham, Y. Shen, R. Martin, Angew. Chem. Int. Ed., 2017, 56, 10915-10919.
[57]	J.-H. Ye, M. Miao, H. Huang, S.-S. Yan, Z.-B. Yin, W.-J. Zhou, D.-G. Yu, Angew. Chem. Int. Ed., 2017, 56, 15416-15420.
[58]	L.-L. Liao, G.-M. Cao, J.-H. Ye, G.-Q. Sun, W.-J. Zhou, Y.-Y. Gui, S.-S. Yan, G. Shen, D.-G. Yu, J. Am. Chem. Soc., 2018, 140, 17338-17342.
[59]	J. Hou, A. Ee, H. Cao, H.-W. Ong, J.-H. Xu, J. Wu, Angew. Chem. Int. Ed., 2018, 57, 17220-17224.
[60]	T. Ju, Q. Fu, J.-H. Ye, Z. Zhang, L.-L. Liao, S.-S. Yan, X.-Y. Tian, S.-P. Luo, J. Li, D.-G. Yu, Angew. Chem. Int. Ed., 2018, 57, 13897-13901.
[61]	X. Fan, X. Gong, M. Y. Ma, R. Wang, P. J. Walsh, Nat. Commun., 2018, 9, 4936.
[62]	H. Wang, Y. Gao, C. Zhou, G. Li, J. Am. Chem. Soc., 2020, 142, 8122-8129.
[63]	W.-J. Zhou, Z.-H. Wang, L.-L. Liao, Y.-X. Jiang, K.-G. Cao, T. Ju, Y. Li, G.-M. Cao, D.-G. Yu, Nat. Commun., 2020, 11, 3263.
[64]	H. Huang, J.-H. Ye, L. Zhu, C.-K. Ran, M. Miao, W. Wang, H. Chen, W.-J. Zhou, Y. Lan, B. Yu, D.-G. Yu, CCS Chem., 2020, 2, 1746-1756.
[65]	T. Ju, Y.-Q. Zhou, K.-G. Cao, Q. Fu, J.-H. Ye, G.-Q. Sun, X.-F. Liu, L. Chen, L.-L. Liao, D.-G. Yu, Nat. Catal., 2021, 4, 304-311.
[66]	P. J. Riss, S. Lu, S. Telu, F. I. Aigbirhio, V. W. Pike, Angew. Chem. Int. Ed., 2012, 51, 2698-2702.
[67]	D.-T. Yang, M. Zhu, Z. J. Schiffer, K. Williams, X. Song, X. Liu, K. Manthiram, ACS Catal., 2019, 9, 4699-4705.
[68]	Y. Basel, A. Hassner, J. Org. Chem., 2000, 65, 6368-6380.
[69]	Z. Zhang, L.-L. Liao, S.-S. Yan, L. Wang, Y.-Q. He, J.-H. Ye, J. Li, Y.-G. Zhi, D.-G. Yu, Angew. Chem. Int. Ed., 2016, 55, 7068-7072.
[70]	L. Song, L. Zhu, Z. Zhang, J.-H. Ye, S.-S. Yan, J.-L. Han, Z.-B. Yin, Y. Lan, D.-G. Yu, Org. Lett., 2018, 20, 3776-3779.

可见光催化二氧化碳与苄位卤代物的羧基化: 温和条件且无过渡金属

Visible-light photoredox-catalyzed carboxylation of benzyl halides with CO₂: Mild and transition-metal-free

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 10

参考文献

相关文章 15

编辑推荐

Metrics

[1]	王思恺, 闵祥婷, 乔波涛, 颜宁, 张涛. 单原子催化: 追寻催化领域的“圣杯”[J]. 催化学报, 2023, 52(9): 1-13.
[2]	邹心仪, 顾均. 酸性条件下二氧化碳高效电还原策略[J]. 催化学报, 2023, 52(9): 14-31.
[3]	李轩, 蒋兴星, 孔艳, 孙建桔, 胡琪, 柴晓燕, 杨恒攀, 何传新. GaN/In₂O₃的界面工程用于高效电催化CO₂还原制备甲酸[J]. 催化学报, 2023, 50(7): 314-323.
[4]	肖汉至, 于博, 颜思顺, 章炜, 李茜茜, 鲍莹, 罗书平, 叶剑衡, 余达刚. 可见光催化二氧化碳参与非活化烯烃1,3-双羧基化反应[J]. 催化学报, 2023, 50(7): 222-228.
[5]	李慧珍, 陈艳蕾, 牛青, 王小凤, 刘哲源, 毕进红, 于岩, 李留义. 具有定向电荷传递能力的晶态线型聚酰亚胺材料驱动光催化CO₂还原[J]. 催化学报, 2023, 49(6): 152-159.
[6]	李孜孜, 王嘉蔚, 黄衍钧, 欧阳钢锋. 钴(II)酞菁全氟化策略用于提升非贵金属体系中光催化还原CO₂性能[J]. 催化学报, 2023, 49(6): 160-167.
[7]	杨焕焕, 李诗颖, 许群. 铜基催化剂电催化高效还原CO₂制备C₂₊产物的调控策略[J]. 催化学报, 2023, 48(5): 32-65.
[8]	李静静, 张锋伟, 詹新雨, 郭河芳, 张涵, 昝文艳, 孙振宇, 张献明. 酞菁镍分子结构的精确设计: 优化电子和空间效应用于CO₂电还原[J]. 催化学报, 2023, 48(5): 117-126.
[9]	危长城, 张雯娜, 杨阔, 柏秀, 徐舒涛, 李金哲, 刘中民. CO₂作为化学品原料的高效利用途径: 与烷烃耦合反应[J]. 催化学报, 2023, 47(4): 138-149.
[10]	詹麒尼, 帅婷玉, 徐慧民, 黄陈金, 张志杰, 李高仁. 单原子催化剂的合成及其在电化学能量转换中的应用[J]. 催化学报, 2023, 47(4): 32-66.
[11]	孔艳, 蒋兴星, 李轩, 孙建桔, 胡琪, 柴晓燕, 杨恒攀, 何传新. 超高质量活性的碳纳米纤维包覆铋纳米颗粒用于高效二氧化碳电还原制甲酸[J]. 催化学报, 2023, 45(2): 95-106.
[12]	沙峰, 唐珊, 汤驰洲, 冯振东, 王集杰, 李灿. ZnZrO_x固溶体催化剂表面羟基在CO₂加氢制甲醇中的作用[J]. 催化学报, 2023, 45(2): 162-173.
[13]	卞磊, 张紫阳, 田昊, 田娜娜, 马智, 王中利. 具有丰富晶界的铜催化剂在气-液平衡扩散电极上高效电还原CO₂制C₂H₄[J]. 催化学报, 2023, 54(11): 199-211.
[14]	林莉, 何潇洋, 谢顺吉, 王野. CO₂电催化转化迈向大规模化的挑战与展望[J]. 催化学报, 2023, 53(10): 1-7.
[15]	钟蕤羽, 梁玉洁, 黄菲, 梁诗诺, 刘升卫. 一维g-C₃N₄/二维Ti₃C₂T_x界面调制促进光催化CO₂还原活性与选择性[J]. 催化学报, 2023, 53(10): 109-122.

可见光催化二氧化碳与苄位卤代物的羧基化: 温和条件且无过渡金属

Visible-light photoredox-catalyzed carboxylation of benzyl halides with CO2: Mild and transition-metal-free

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 10

参考文献

相关文章 15

编辑推荐

Metrics

Visible-light photoredox-catalyzed carboxylation of benzyl halides with CO₂: Mild and transition-metal-free