Chinese Journal of Organic Chemistry >
Regioselective C(2) Methylthiolation and d3-Methylthiolation of Indoles Based on Dimethyl Sulfoxide (DMSO-d6) Reagents
Received date: 2023-10-26
Revised date: 2023-12-24
Online published: 2024-01-18
Supported by
State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology(SKL202102); Natural Science Foundation of Shanxi Province(20210302124123); Natural Science Foundation of Shanxi Province(202303021211033)
Cu(OAc)2 mediated C(2)-selective d3-methylthiolation and methylthiolation of indoles were developed. With the choice of dimethyl sulfoxide (DMSO) as sulfur source and solvent, methylthiolation reaction could be achieved in moderate to good yields, and d3-methylthiolated products could also be obtained with DMSO-d6 as reagent just by prolong the reaction time. Moreover, this methylthiolation didn’t depend on high temperature, and radical pathway might be involved in this transformation.
Key words： copper; indole; d3-methylthiolation; methylthiolation; dimethyl sulfoxide (DMSO)
Juan Zhang , Yisen Wang , Yu Tian , Jing Xu , Wenchao Gao , Honghong Chang , Fanhui Meng , Peng Yang . Regioselective C(2) Methylthiolation and d3-Methylthiolation of Indoles Based on Dimethyl Sulfoxide (DMSO-d6) Reagents[J]. Chinese Journal of Organic Chemistry, 2024 , 44(5) : 1576 -1583 . DOI: 10.6023/cjoc202310026
| [1] | (a) Jiang, X. Sulfur Chemistry, Springer, Switzerland, 2019, p. 475. |
| [1] | (b) Feng, M.; Tang, B.; Liang, H. S.; Jiang, X. Curr. Top. Med. Chem. 2016, 16, 1200. |
| [1] | (c) Dunbar, K. L.; Scharf, D. H.; Litomska, A.; Hertweck, C. Chem. Rev. 2017, 117, 5521. |
| [1] | (d) Ilardi, E. A.; Vitaku, E.; Njardarson, J. T. J. Med. Chem. 2014, 57, 2832. |
| [2] | (a) Wang, N.; Saidhareddy, P.; Jiang, X. Nat. Prod. Rep. 2020, 37, 246. |
| [2] | (b) Li, X.; Wang, X.; Li, Y.; Xiao, J.; Du, Y. Org. Biomol. Chem. 2022, 20, 4471. |
| [3] | (a) Shen, C.; Qiao, J.; Zhao, L.; Zheng, K.; Jin, J.; Zhang, P. Catal. Commun. 2017, 92, 114. |
| [3] | (b) Li, H. L.; Kuninobu, Y.; Kanai, M. Angew. Chem., Int. Ed. 2017 129, 1517. |
| [3] | (c) Chen, S.; Guo, X.; Hou, H.; Geng, S.; Liu, Z.; He, Y.; Xue, X.; Feng, Z. Angew. Chem., Int. Ed. 2023, 62, e202303470. |
| [4] | (a) Zhang, C.; Zhou, Y.; Huang, J.; Tu, C.; Zhou, X.; Yin, G. Org. Biomol. Chem. 2018, 16, 6316. |
| [4] | (b) Hu, L.; Wang, D.; Chen, X.; Yu, L.; Yu, Y.; Tan, Z.; Zhu, G. Org. Biomol. Chem. 2017, 15, 5674. |
| [4] | (c) Wang, M.; Qiao, Z.; Zhao, J.; Jiang, X. Org. Lett. 2018, 20, 6193. |
| [4] | (d) Zhang, B.; Li, X.; Li, X.; Sun, F.; Du, Y. Chin. J. Chem. 2020, 39, 887. |
| [5] | (a) Chen, X.; Hao, X. S.; Goodhue, C. E.; Yu, J. Q. J. Am. Chem. Soc. 2006, 128, 6790. |
| [5] | (b) Dai, C.; Xu, Z.; Huang, F.; Yu, Z.; Gao, Y.-F. J. Org. Chem. 2012, 77, 4414. |
| [5] | (c) Chu, L.; Yue, X.; Qing, F.-L. Org. Lett. 2010, 12, 1644. |
| [5] | (d) Liu, F. Org. Biomol. Chem. 2023, 21, 1153. |
| [6] | (a) Wu, X.-F.; Natteb, K. Adv. Synth. Catal. 2016, 358, 336. |
| [6] | (b) Tashrifi, Z.; Khanaposhtani, M. M.; Larijani, B.; Mahdavi, M. Adv. Synth. Catal. 2020, 362, 65. |
| [6] | (c) Lu, H.; Tong, Z.; Peng, L.; Wang, Z.; Yin, S.-F.; Kambe, N.; Qiu, R. Top Curr. Chem. 2022, 380, 55. |
| [7] | (a) Tian, Y.; Zhang, J. ; Gao, W.; Chang, H. Chin. J. Org. Chem. 2023, 43, 2391 (in Chinese). |
| [7] | ( 田钰, 张娟, 高文超, 常宏宏, 有机化学, 2023, 43, 2391.) |
| [7] | (b) Sun, Q.; Soule, J.-F. Chem. Soc. Rev. 2021, 50, 10806. |
| [8] | For review see: Li, X.; Wang, X.; Li, Y.; Xiao, J.; Du, Y. Org. Biomol. Chem. 2022, 20, 4471. |
| [9] | (a) Zhang, Z.; Chen, P.; Liu, G. Chem. Soc. Rev. 2022, 51, 1640. |
| [9] | (b) Li, Z.-L. Fang, G.-C.; Gu, Q.-S.; Liu, X.-Y. Chem. Soc. Rev. 2020, 49, 32. |
| [10] | (a) Zheng. C.; You. S.-L. Nat. Prod. Rep. 2019, 36, 1589. |
| [10] | (b) Leitch. J. A.; Bhonoah. Y.; Frost. C. G. ACS Catal. 2017, 7, 5618. |
| [10] | (c) Vitaku, E.; Smith, D. T.; Njardarson, J. T. J. Med. Chem. 2014, 57, 10257. |
| [11] | (a) Ankade, S. B.; Shabade, A. B.; Soni, V.; Punji, B. ACS Catal. 2021, 11, 3268. |
| [11] | (b) Sandtorv, A. H. Adv. Synth. Catal. 2015, 357, 2403. |
| [11] | (c) Joucla, L.; Djakovitch, L. Adv. Synth. Catal. 2009, 351, 673. |
| [11] | (d) Wen, J.; Shi, Z. Acc. Chem. Res. 2021, 54, 1723. |
| [11] | (e) Liu, Y.-H.; Xie, P.-P.; Liu, L.; Fan, J.; Zhang, Z.-Z.; Hong, X.; Shi, B.-F. J. Am. Chem. Soc. 2021, 143, 19112. |
| [12] | (a) Gensch, T.; Klauck, F. J. R.; Glorius, F. Angew. Chem., Int. Ed. 2016, 55, 11287. |
| [12] | (b) Zou, J.-F.; Huang, W.-S.; Li, L.; Xu, Z.; Zheng, Z.-J.; Yang, K.-F.; Xu, L.-W. RSC Adv. 2015, 5, 30389. |
| [13] | Wu, Y.; Ding, H.; Zhao, M.; Ni, Z.-H.; Cao, J.-P. Green Chem. 2020, 22, 4906. |
| [14] | Zhang, L.-Y.; Wu, Y.-H.; Wang, N.-X.; Gao, X.-W.; Yan, Z.; Xu, B.-C.; Liu, N.; Wang, B.-Z.; Xing, Y. Eur. J. Org. Chem. 2021, 2021, 1446. |
| [15] | Sharma, P.; Rohilla, S.; Jain, N. J. Org. Chem. 2015, 80, 4116. |
| [16] | Huang, J.; Sun, W.-W.; Li, J.-Q.; Ma, A.-D.; Liu, J.-K.; Wu, B. Org. Lett. 2023, 25, 528. |
| [17] | (a) Barreiro, E. J.; Kümmerle, A. E.; Fraga, C. A. M. Chem. Rev. 2011, 111, 5215. |
| [17] | (b) Sch?nherr, H.; Cernak, T. Angew. Chem., Int. Ed. 2013, 52, 12256. |
| [18] | Goyal, V.; Sarki, N.; Narani, A.; Naik, G.; Natte, K.; Jagadeesh, R. V. Coord. Chem. Rev. 2023, 474, 214827. |
| [19] | Schmidt, C. Nat. Biotechnol. 2017, 35, 493. |
| [20] | (a) Gao, Q.; Shang, Y.; Song, F.; Ye, J.; Liu, Z.-S.; Li, L.; Cheng, H.-G.; Zhou, Q. J. Am. Chem. Soc. 2019, 141, 15986. |
| [20] | (b) Wang, M.; Zhao, Y.; Zhao, Y.; Shi, Z. Sci. Adv. 2020, 6, eaba0946. |
| [21] | (a) Cui, X.; Liu, X.; Wang, X.; Tian, W.; Wei, D.; Huang, G. ChemistrySelect 2017, 2, 8607. |
| [21] | (b) Dighe, S. U.; Samanta, S. K.; Kolle, S.; Batra, S. Tetrahedron 2017, 73, 2455. |
| [22] | (a) Chen, Z.; Cao, G.; Zhang, F.; Li, H.; Xu, J.; Miao, M.; Ren, H. Synlett 2017, 28, 1795. |
| [22] | (b) Rastogi, G. K.; Deka, B.; Deb, M. L.; Baruah, P. K. Eur. J. Org. Chem. 2020, 2020, 424. |
/
| 〈 |
|
〉 |
