Recent Advances in the Mesylation

doi:10.6023/A25010015

Acta Chimica Sinica ›› 2025, Vol. 83 ›› Issue (3): 274-286.DOI: 10.6023/A25010015 Previous Articles Next Articles

Review

甲磺酰化反应的最新研究进展

周泉^a, 蒋佳怡^b, 罗年华^b^,^*(), 黄家翩^b^,^*

a 台州学院药学院&高等研究院台州 318000
b 赣南医科大学药学院江西省中药药理重点实验室赣州 341000

投稿日期:2025-01-10 发布日期:2025-02-27

作者简介:

周泉, 博士, 台州学院药学院讲师. 2020年9月复旦大学博士后出站后加入台州学院. 至今为止, 以第一作者身份在Org. Lett., Org. Chem. Front., J. Org. Chem., Org. Biomol. Chem.等期刊发表SCI论文近10篇, 获中国授权专利1项.

罗年华, 博士, 赣南医科大学药学院, 副教授, 硕导. 2012年6月博士毕业于中山大学药学院, 有机化学专业. 博士毕业后进入广州龙沙研发中心, 从事药物中间体合成工作, 任高级有机合成研究员. 2013年9月进入上饶师范学院工作. 2018年7月进入赣南医科大学工作. 研究方向为有机合成和药物合成. 主持参与省级以上课题多项. 至今为止, 以第一作者或通讯作者身份在J. Org. Chem., Organometallics, Eur. J. Org. Chem., Synthesis等期刊发表SCI论文10余篇, 获中国授权专利多项.

黄家翩, 博士, 赣南医科大学药学院讲师. 2017年6月硕士毕业后, 加入中科院上海有机化学研究所游书力研究员课题组从事研究助理工作. 2019年8月进入台州学院工作. 2024年6月获得江西师范大学有机化学专业博士学位. 2024年9月进入赣南医科大学药学院工作. 至今为止, 以第一作者身份在Nat. Commun., ACS Catal., Sci. China Chem., Org. Lett., Org. Chem. Front., J. Org. Chem., Adv. Synth. Catal.等期刊发表SCI论文近20篇, 获中国授权专利多项.

Recent Advances in the Mesylation

Quan Zhou^a, Jiayi Jiang^b, Nianhua Luo^b(), Jiapian Huang^b

a School of Pharmaceutical Sciences & Institute for Advanced Studies, Taizhou University, Taizhou 318000, China
b Jiangxi Province Key Laboratory of Pharmacology of Traditional Chinese Medicine, College of Pharmacy, Gannan Medical University, Ganzhou 341000, China

Received:2025-01-10 Published:2025-02-27
Contact: ^*E-mail: huangjiapian@163.com

In recent years, organic reactions involving mesylation have attracted the attention of organic chemists and have made great progress. The sources of methylsulfonyl group mainly include: (1) methylsulfonyl chloride; (2) methylsulfinate salts; (3) dimethyl sulfoxide; (4) dimethyl sulfite; (5) SO₂ and methyl sources in situ generating. Mesylation can be achieved by means of transition-metal-free catalysis, transition metal catalysis, photocatalysis, electrocatalysis, etc. In this review, the applications of mesylation in recent years are summarized. The photocatalysis or electrocatalysis of radical methylsulfonation are emphasized. Additionally, mesylation reactions have been aroused considerable interests both from methylsulfonyl structural standpoint and its application in drugs. Given the increasing application of methylsulfonyl group in the development of drugs and unarguable importance of methylsulfonyl compounds in medicinal chemistry and agrochemistry, it is no doubt that the methylsulfonyl skeleton is a bioactive molecule and is currently in the “emerging mesylation motifs”. Although the synthesis and application of structurally diverse methylsulfonyl compounds have been witnessed in the past decade, the most widely used methods for the preparation of these compounds include all kinds of modern techniques with various methylsulfonyl reagent, which can be generated from various kinds of precursors. For the transition metal-catalyzed synthesis of methylsulfonyl compounds, some common metal salts (such as copper, copper, palladium, iron, nickel) are used as catalysts. Moreover, the visible-light synergistic transition metal catalysis strategy is a simple and efficient method for the construction of methylsulfonyl compounds, and the asymmetric synthesis of methylsulfonyl compounds can be achieved in the presence of chiral ligands. In multi-component reactions, SO₂-insertion has some advantages that cannot be achieved by traditional mesylated reagents for the direct mesylation of alkenes or alkynes. Despite the remarkable achievements in the synthesis of methylsulfonyl compounds, there are still many issues that need to be addressed. For instance, multi-component mesylation reactions are rarely applied in electrocatalysis, asymmetric catalysis fields and flow chemistry. Hopefully, mesylation can gradually appear in photo- and electro-catalyzed radical chemistry, and the related asymmetric reactions will also get more attention and development in the near future.

Key words: mesylation, methylsulfonyl, methylsulfonyl compounds, transition-metal catalyzed, photo-/electro-catalyzed, radical reaction

Cite this article

Quan Zhou, Jiayi Jiang, Nianhua Luo, Jiapian Huang. Recent Advances in the Mesylation[J]. Acta Chimica Sinica, 2025, 83(3): 274-286.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 15

Figure 1. Active molecule containing methyl sulfonyl group fragment

Figure 2. Methylsulfonyl compounds were prepared by reverse synthesis analysis

Figure 3. Methylsulfonyl chloride as a source of methylsulfonyl group involved in the mesylation reaction

Figure 4. Sodium methylsulfinate as a source of methylsulfonyl group participates in the o-mesylation of aromatic hydrocarbons

Figure 5. Sodium methylsulfinate as a source of methylsulfonyl group participates in the difunctionalization of olefins

Figure 6. Sodium methylsulfinate as a source of methylsulfonyl group participates in the mesylation of alkynenes

Figure 7. Sodium methylsulfinate as a source of methylsulfonyl group participates in the mesylation of alkenes/alkynes

Figure 8. Sodium methylsulfinate as a source of methylsulfonyl group coupled with alkyl/aryl groups

Figure 9. Sodium methylsulfinate as a source of methylsulfonyl group participates in the mesylation of pyridines

Figure 10. Dimethyl sulfoxide as a source of methylsulfonyl group involved in the mesylation reactions

Figure 11. Dimethyl sulfite or methylsulfonimine as a source of methylsulfonyl group involved in the mesylation reactions

Figure 12. Methylsulfonyl compounds were prepared by reverse synthesis analysis of three components

Figure 13. Organic peroxides as methyl sources and combine with sulfur dioxide to form methylsulfonyl compounds

Figure 14. Methyl halides as methyl sources and combine with sulfur dioxide to form methylsulfonyl compounds

Figure 15. (Diacetoxyiodo)benzenes, methylsulfonium salts or methyl sulfides as methyl sources and combine with SO2 to form methylsulfonyl compounds

References 33

[1]	(a) Schonherr, H.; Cernak, T. Angew. Chem. Int. Ed. 2013, 52, 12256.
	(b) Sun, S.; Fu, J. Bioorg. Med. Chem. Lett. 2018, 28, 3283.
	(c) Huang, J.; Chen, Z.; Wu, J. ACS Catal. 2021, 11, 10713.
[2]	(a) Frampton, J. E.; Basset-Séguin, N. Drugs 2018, 78, 1145. doi: 10.1007/s40265-018-0948-9 pmid: 30030732
	(b) Sturino, C. F.; O'Neill, G.; Lachance, N.; Boyd, M.; Berthelette, C.; Labelle, M.; Li, L.; Roy, B.; Scheigetz, J.; Tsou, N.; Aubin, Y.; Bateman, K. P.; Chauret, N.; Day, S. H.; Lévesque, J.; Seto, C.; Silva, J. H.; Trimble, L. A.; Carriere, M.; Denis, D.; Greig, G.; Kargman, S.; Lamontagne, S.; Mathieu, M.; Sawyer, N.; Slipetz, D.; Abraham, W. M.; Jones, T.; McAuliffe, M.; Piechuta, H.; Nicoll-Griffith, D. A.; Wang, Z.; Zamboni, R.; Young, R. N.; Metters, K. M. J. Med. Chem. 2007, 50, 794. pmid: 30030732
	(c) Prasit, P.; Wang, Z.; Brideau, C.; Chan, C.-C.; Charleson, S.; Cromlish, W.; Ethier, D.; Evans, J. F.; Ford-Hutchinson, A. W.; Gauthier, J. Y.; Gordon, R.; Guay, J.; Gresser, M.; Kargman, S.; Kennedy, B.; Leblanc, Y.; Léger, S.; Mancini, J.; O'Neill, G. P.; Ouellet, M.; Percival, M. D.; Perrier, H.; Riendeau, D.; Rodger, I.; Tagari, P.; Thérien, M.; Vickers, P.; Wong, E.; Xu, L.-J.; Young, R. N.; Zamboni, R. et al. Bioorg. Med. Chem. Lett. 1999, 9, 1773. pmid: 30030732
	(d) Feng, M.; Tang, B.; Liang, S. H.; Jiang, X. Curr. Top. Med. Chem. 2016, 16, 1200. pmid: 30030732
	(e) Wen, Y.; Zhang, S.; Hou, G.; Yu, Y.; Gao, J. Chin. J. Org. Chem. 2016, 36, 642 (in Chinese). pmid: 30030732
	(温彦鹏, 张爽, 侯广峰, 于颖慧, 高金胜, 有机化学, 2016, 36, 642). doi: 10.6023/cjoc201508008 pmid: 30030732
	(f) Wu, Y.; Yan, Y.; Liao, W. Chin. J. Org. Chem. 2023, 43, 3713 (in Chinese). pmid: 30030732
	吴宇恒, 颜岩, 寮渭巍, 有机化学, 2023, 43, 3713). doi: 10.6023/cjoc202305014 pmid: 30030732
[3]	(a) Zhao, W.; Liu, Y. Chlor-Alkali Industry 1999, (5), 40 (in Chinese).
	(赵维生, 刘雅娟, 氯碱工业, 1999, (5), 40.)
	(b) Hell, S. M.; Meyer, C. F.; Misale, A.; Sap, J. B. I.; Christensen, K. E.; Willis, M. C.; Trabanco, A. A.; Gouverneur, V. Angew. Chem. Int. Ed. 2020, 59, 11620.
	(c) Wu, D.; Jiang, M.; Wang, J.-J.; Yu, W. Org. Lett. 2023, 25, 2073.
[4]	Johnson, T. C.; Elbert, B. L.; Farley, A. J. M.; Gorman, T. W.; Genicot, C.; Lallemand, B.; Pasau, P.; Flasz, J.; Castro, J. L.; MacCoss, M.; Dixon, D. J.; Paton, R. S.; Schoﬁeld, C. J.; Smith, M. D.; Willis, M. C. Chem. Sci. 2018, 9, 629. doi: 10.1039/c7sc03891g pmid: 29629128
[5]	Higham, J. I.; Ma, T.-K.; Bull, J. A. Org. Lett. 2023, 25, 5285. doi: 10.1021/acs.orglett.3c01783 pmid: 37439636
[6]	(a) Zheng, Y.; You, Y.; Shen, Q.; Zhang, J.; Liu, L.; Duan, X.-H. Org. Chem. Front. 2020, 7, 2069.
	(b) Vega, K. B.; Delgado, J. A. C.; Pugnal, L. V. B. L.; Konig, B.; Correia, J. T. M.; Paixao, M. W. Chem. Eur. J. 2023, 29, e202203625.
[7]	(a) Liu, M.-S.; Shu, W. JACS Au 2023, 3, 1321.
	(b) Xia, S.; Wu, L.; Zhai, G.; Wang, Z.; Wu, J. Org. Chem. Front. 2023, 10, 4002.
	(c) Xu, Y.; Wang, S.; Liu, Z.; Guo, M.; Lei, A. Chem. Commun. 2023, 59, 3707.
	(d) Rao, W.-H.; Gao, C.; Jiang, L.-L.; Zhou, F.-Y.; Liu, J.-F.; Zou, G.-D. J. Org. Chem. 2024, 89, 12681.
[8]	Lipp, B.; Kammer, L. M.; Kücükdisli, M.; Luque, A.; Kühlborn, J.; Pusch, S.; Matulevičiūtė, G.; Schollmeyer, D.; Šačkus, A.; Opatz, T. Chem. Eur. J. 2019, 25, 8965.
[9]	Chen, Y.; Zhu, K.; Huang, Q.; Lu, Y. Chem. Sci. 2021, 12, 13564. doi: 10.1039/d1sc04320j pmid: 34777776
[10]	Wang, L.; Ma, R.; Sun, J.; Zheng, G.; Zhang, Q. Chem. Sci. 2022, 13, 3169.
[11]	Li, M.-D.; Wang, Z.-H.; Zhu, H.; Wang, X.-R.; Wang, J.-R.; Lin, T.-Y. Angew. Chem. Int. Ed. 2023, 62, e202313911.
[12]	Yin, Z.; Yu, Y.; Mei, H.; Han, J. Green Chem. 2021, 23, 3256.
[13]	Chandu, P.; Mallick, M.; Srinivasu, V.; Sureshkumar, D. Chem. Eur. J. 2024, 30, e202303187.
[14]	Liu, Q.-Q.; Li, J.-Z.; Wang, Y.-J.; Leng, Y.-N.; Huang, Y.-W.; Meng, X.-C.; Leng, B.-R.; Wang, D.-C.; Zhu, Y.-L. J. Org. Chem. 2023, 88, 17227.
[15]	He, J.; Chen, G.; Zhang, B.; Li, Y.; Chen, J.-R.; Xiao, W.-J.; Liu, F.; Li, C. Chem 2020, 6, 1149.
[16]	Granados, A.; Cabrera-Afonso, M. J.; Escolano, M.; Badir, S. O.; Molander, G. A. Chem Catal. 2022, 2, 898.
[17]	Mdluli, V.; Lehnherr, D.; Lam, Y.-H.; Ji, Y.; Newman, J. A.; Kim, J. Adv. Synth. Catal. 2023, 365, 3876.
[18]	Qin, S.; Yang, M.; Xu, M.; Peng, Z.-H.; Cai, J.; Wang, S.; Gao, H.; Zhou, Z.; Hashmi, A. S. K.; Yi, W.; Zeng, Z. Nat. Commun. 2024, 15, 7428.
[19]	Huang, M.-H.; Zhu, C.-F.; He, C.-L.; Zhu, Y.-L.; Hao, W.-J.; Wang, D.-C.; Tu, S.-J.; Jiang, B. Org. Chem. Front. 2018, 5, 1643.
[20]	Zhang, J.; Cheng, S.; Cai, Z.; Liu, P.; Sun, P. J. Org. Chem. 2018, 83, 9344. doi: 10.1021/acs.joc.8b01265 pmid: 29969266
[21]	Chang, M.-Y.; Chen, H.-Y.; Tsai, Y.-L. Org. Lett. 2019, 21, 1832.
[22]	(a) Xin, Y.-H.; Guo, Y.-Q.; Zhang, X.-G.; Deng, C.-L. J. Org. Chem. 2021, 86, 17496.
	(b) Zhuang, J.-Q.; Guo, Y.-Q.; Deng, C.-L.; Zhang, X.-G.; Tu, H.-Y. J. Org. Chem. 2023, 88, 10753.
[23]	Singha, T.; Bapat, N. A.; Mishra, S. K.; Hari, D. P. Org. Lett. 2024, 26, 6396.
[24]	(a) He, F.-S.; Gong, X.; Rojsitthisak, P.; Wu, J. J. Org. Chem. 2019, 84, 13159.
	(b) Tian, X.; Chen, L.; Zhu, T.; Wu, J. Org. Chem. Front. 2023, 10, 4821.
[25]	He, Y.; Yang, J.; Liu, Q.; Zhang, X.; Fan, X. J. Org. Chem. 2020, 85, 15600. doi: 10.1021/acs.joc.0c02368 pmid: 33180489
[26]	He, F.-S.; Zhang, M.; Zhang, M.; Luo, X.; Wu, J. Org. Chem. Front. 2021, 8, 3746.
[27]	Hou, X.; Liu, H.; Huang, H. Nat. Commun. 2024, 15, 1480.
[28]	Wang, Z.; Ma, R.; Gu, C.; He, X.; Shi, H.; Bai, R.; Shi, R. Adv. Sci. 2024, 11, 2406228.
[29]	Nolla-Saltiel, R.; Ariki, Z. T.; Schiele, S.; Alpin, J.; Tahara, Y.; Yokogawa, D.; Nambo, M.; Crudden, C. M. Nat. Chem. 2024, 16, 1445.
[30]	For some selected examples: (a) Liu, G.; Fan, C.; Wu, J. Org. Biomol. Chem. 2015, 13, 1592.
	(b) Zheng, D.; Wu, J. Sulfur Dioxide Insertion Reactions for Organic Synthesis, Nature Springer, Berlin, 2017.
	(c) Qiu, G.; Zhou, K.; Wu, J. Org. Chem. Front. 2018, 5, 691.
	(d) Qiu, G.; Lai, L.; Cheng, J.; Wu, J. Chem. Commun. 2018, 54, 10405.
	(e) Qiu, G.; Zhou, K.; Wu, J. Chem. Commun. 2018, 54, 12561.
	(f) Ye, S.; Qiu, G.; Wu, J. Chem. Commun. 2019, 55, 1013.
	(g) Ye, S.; Yang, M.; Wu, J. Chem. Commun. 2020, 56, 4145.
	(h) Huang, J.; Liu, F.; Zeng, L.-H.; Li, S.; Chen, Z.; Wu, J. Nat. Commun. 2022, 13, 7081.
	(i) Huang, J.; Wang, C.; Wang, X.; Zhou, X.; Xiao, W.; Wu, J. Sci. China Chem. 2025, 68, 257.
[31]	(a) Zhu, T.; Rojsitthisak, P.; Wu, J. Org. Chem. Front. 2020, 7, 4050.
	(b) Li, W.; Wang, C.; Zhu, T.; Liu, G.; Wu, J. Chem. Commun. 2024, 60, 8212.
[32]	He, F.-S.; Bao, P.; Tang, Z.; Yu, F.; Deng, W.-P.; Wu, J. Org. Lett. 2022, 24, 2955.
[33]	Gong, X.; Wang, M.; Ye, S.; Wu, J. Org. Lett. 2019, 21, 1156.

甲磺酰化反应的最新研究进展

Recent Advances in the Mesylation

RichHTML

PDF

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 15

References 33

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Kangkui Li, Xianyang Long, Yue Huang, Shifa Zhu. Recent Advances in Visible Light Induced Radical 1,2-Functionalization of Alkynes [J]. Acta Chimica Sinica, 2024, 82(6): 658-676.
[2]	Hao Liu, Xuli Xu, Yong Guo, Xiaohui Liu, Yanqin Wang. Efficient Electro-catalytic Reductive Amination of Aldehyde over Ru Deposited on Nickel Phosphate [J]. Acta Chimica Sinica, 2024, 82(5): 477-485.
[3]	Zhao, Yong, Li, Shihong, Zhang, Miaomiao, Liu, Feng. Synthesis of β,γ-Unsaturated Esters and γ-Ketone Esters with Amino Acid Ester-Derived Katritzky Salts [J]. Acta Chimica Sinica, 2019, 77(9): 916-921.
[4]	Gu Zhengyang, Ji Shunjun. Recent Advances in Cobalt Catalyzed Isocyanide Coupling Reactions [J]. Acta Chim. Sinica, 2018, 76(5): 347-356.
[5]	Chen Dong, Ji Meishan, Yao Yingming, Zhu Chen. Difunctionalization of Unactivated Alkenes through SCF₃ Radical-triggered Distal Functional Group Migration [J]. Acta Chimica Sinica, 2018, 76(12): 951-955.
[6]	Zhang Jing, Chen Yiyun. Visible-Light-Induced Carboxyl and Alkoxyl Radical Generations and Reactions [J]. Acta Chim. Sinica, 2017, 75(1): 41-48.
[7]	Wang Dehong, Zhang Long, Luo Sanzhong. Photo-induced Catalytic Asymmetric Free Radical Reactions [J]. Acta Chim. Sinica, 2017, 75(1): 22-33.
[8]	Yu Kuan, Gao Beiling, Ding Hanfeng. Asymmetric Total Synthesis and Absolute Configuration Reassignment of Indole Alkaloid (+)-Alsmaphorazine D [J]. Acta Chim. Sinica, 2016, 74(5): 410-414.
[9]	Zhang Ling, Zhang Peizhi, Xue Jianfei, Sun Wangbin, Zou Jianping. Manganese Acetate-Mediated Phosphorylation of Indoles [J]. Acta Chim. Sinica, 2016, 74(10): 811-818.
[10]	Ouyang Kunbing, Xi Zhenfeng. Roles of Bases in Transition-Metal Catalyzed Organic Reactions [J]. Acta Chimica Sinica, 2013, 71(01): 13-25.
[11]	CHE Hai-Ying, YANG Jun, WU Kai, WANG Jiu-Lin, NU Li-Yan-Na. Effect of Lithium Bis(trifluoromethylsulfonyl)imide on the High- temperature Behavior of LiFePO₄ Positive Electrode [J]. Acta Chimica Sinica, 2011, 69(11): 1287-1292.
[12]	SUN Cui-Hong,ZENG Yan-Li^1,2,MENG Ling-Peng,ZHENG Shi-Jun^*,1. Reaction Mechanisms and Topological Studies of ElectronDensity on the Reaction of CH₂SH Radical and Cl Atom [J]. Acta Chimica Sinica, 2005, 63(4): 295-300.
[13]	YAN Ge-Xin, LIU Wei-Ping, GAO Wen-Gui, HU Chang-Yi, YU Wei, LIANG Guang. Thermal Decomposition Behavior of Tris(2,4-pentanedionato-O, O') Iridium(Ⅲ) [J]. Acta Chimica Sinica, 2004, 62(19): 1901-1906.
[14]	DING Yuan-Qing, WANG Chao, FANG De-Cai, LIU Ruo-Zhuang. Theoretical Study on the Doublet-State Potential Energy Surface of the Reactions between HCCO(²A″) and O₂(³∑_g^-) [J]. Acta Chimica Sinica, 2004, 62(15): 1373-1378.
[15]	Li Laicai;Tian Anmin;Xu Minghou. Theoretical Study on the Reaction Mechanism of CH_2CH(~2A~＇) Radicals with Ozone [J]. Acta Chimica Sinica, 2003, 61(8): 1256-1260.