Cu(OAc)2-Mediated C—H Bond Dithiolation of Amide-Oxazolines with Aryl Thiols

doi:10.6023/cjoc202009030

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (3): 1098-1107.DOI: 10.6023/cjoc202009030 Previous Articles Next Articles

ARTICLES

醋酸铜促进的酰胺-噁唑啉化合物与芳基硫醇的C—H键双硫代化反应研究

王涛^a^,^b^,^*(), 王晓莎^a, 宋雅雯^a, 霍晶晶^a, 周敬栓^a, 康庆伟^a, 刘澜涛^a^,^b^,^c^,^*()

a 商丘师范学院化学化工学院药物绿色合成河南省工程实验室河南商丘 476000
b 商丘师范学院化学化工学院河南省生物分子识别与传感重点实验室河南商丘 476000
c 郑州大学化学学院郑州 450001

收稿日期:2020-09-12 修回日期:2020-09-30 发布日期:2020-10-22
通讯作者: 王涛, 刘澜涛
基金资助:
河南省高等学校重点科研(19A150035); 河南省科技攻关(192102110222); 河南省高校科技创新人才基金(14HASTIT016); 河南省科技创新杰出人才基金(184100510011)

Cu(OAc)₂-Mediated C—H Bond Dithiolation of Amide-Oxazolines with Aryl Thiols

Tao Wang^a^,^b^,^*(), Xiaosha Wang^a, Yawen Song^a, Jingjing Huo^a, Jingshuan Zhou^a, Qingwei Kang^a, Lantao Liu^a^,^b^,^c^,^*()

a Henan Engineering Laboratory of Green Synthesis for Pharmaceuticals, School of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu, Henan 476000
b Henan Key Laboratory of Biomolecular Recognition and Sensing, School of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu, Henan 476000
c College of Chemistry, Zhengzhou University, Zhengzhou 450001

Received:2020-09-12 Revised:2020-09-30 Published:2020-10-22
Contact: Tao Wang, Lantao Liu
About author:
* Corresponding authors. E-mail: wt67751726@126.com;
liult05@iccas.ac.cn
Supported by:
Key Science Research of Education Committee in Henan Province(19A150035); Key Scienti?c and Technological Project of Henan Province(192102110222); Program for Science & Technology Innovation Talents in Universities of Henan Province(14HASTIT016); Program of Science and Technology Innovation Talents of Henan Province(184100510011)

1. cjoc202009030辅助材料.pdf(22343KB)

Abstract

An efficient copper-mediated dithiolation of C(sp²)—H bonds with aryl thiols was achieved by using amide-oxazo- line as directing group. This strategy gives a variety of functionalized thioethers in moderate to excellent yields (up to 90%) in simple and efficient way. Importantly, the substrate scope is not limited to various substituted phenylamides, and diverse pyridine amides are also compatible. Furthermore, the protocol has been successfully implemented for the gram-scale synthesis as well.

Key words: copper, C—H bond, thiolation, amide-oxazoline, aryl thiols

Cite this article

Tao Wang, Xiaosha Wang, Yawen Song, Jingjing Huo, Jingshuan Zhou, Qingwei Kang, Lantao Liu. Cu(OAc)₂-Mediated C—H Bond Dithiolation of Amide-Oxazolines with Aryl Thiols[J]. Chinese Journal of Organic Chemistry, 2021, 41(3): 1098-1107.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 7

References 19

[1]	Fraústo da Silva, J.R.; Williams, R. J. P. The Biological Chemistry of the Elements, Oxford University Press, New York, 2001.
[2]	(a) Scott, K. A.; Njardarson, J. T. Top. Curr. Chem. 2018, 376, 5.
	(b) Zhao, J.; Jiang, X. Chin. Chem. Lett. 2018, 29, 1079.
[3]	Mellah, M.; Voituriez, A.; Schulz, E. Chem. Rev. 2007, 107, 5133. pmid: 17944520
[4]	Cinar, M. E.; Ozturk, T. Chem. Rev. 2015, 115, 3036. pmid: 25831021
[5]	(a) Khanal, H. D.; Kim, S.H. Lee, Y. R. RSC Adv. 2016, 6, 58501. pmid: 25309983
	(b) Dong, Y.-T.; Jin, Q.; Zhou, L.; Chen, J. Org. Lett. 2016, 18, 5708. pmid: 25309983
	(c) Li, Y.; Zhu, F.; Wang, Z.; Wu, X.-F. Chem. Asian J. 2016, 11, 3503. pmid: 25309983
	(d) Yang, Z.-H.; An, Y.-L.; Chen, Y.; Shao, Z.-Y.; Zhao, S.-Y. Adv. Synth. Catal. 2016, 358, 3869. pmid: 25309983
	(e) Shen, C.; Zhang, P.; Sun, Q.; Bai, S.; Hor, T. S. A.; Liu, X. Chem. Soc. Rev. 2015, 44, 291. pmid: 25309983
[6]	For selected reviews on transition metals catalyzed C—H functionalization, see: (a) Liu, Y.-H.; Xia, Y.-N.; Shi, B.-F. Chin. J. Chem. 2020, 38, 635.
	(b) Shang, M.; Sun, S.-Z.; Wang, H.-L.; Wang, M.-M.; Dai, H.-X. Synthesis 2016, 48, 4381.
	(c) Rao, W.-H.; Shi, B.-F. Org. Chem. Front. 2016, 3, 1028.
	(d) Liu, J.; Chen, G.; Tan, Z. Adv. Synth. Catal. 2016, 358, 1174.
	(e) Hu, Y.; Wang, C. Acta Phys.-Chim. Sin. 2019, 35, 913.
[7]	(a) Jiang, Y.-J.; Liang, G.-H.; Zhang, C.; Loh, T.-P. Eur. J. Org. Chem. 2016, 2016, 3326. pmid: 24488804
	(b) Iwasaki, M.; Nishihara, Y. Dalton Trans 2016, 45, 15278. pmid: 24488804
	(c) Iwasaki, M.; Kaneshika, W.; Tsuchiya, Y.; Nakajima, K.; Nishihara, Y. J. Org. Chem. 2014, 79, 11330. doi: 10.1021/jo502274t pmid: 24488804
	(d) Iwasaki, M.; Lyanaga, M.; Tsuchiya, Y.; Nishimura, Y.; Li, W.-J.; Li, Z.-P.; Nishihara, Y. Chem.-Eur. J. 2014, 20, 2459. pmid: 24488804
[8]	(a) Xie, W.-C.; Li, B.; Wang, B.-Q. J. Org. Chem. 2016, 81, 396. pmid: 24288217
	(b) Yang, Y.-X.; Hou, W.; Qin, L.-H.; Du, J.-J.; Feng, H.-J.; Zhou, B.; Li, Y.-C. Chem.-Eur. J. 2014, 20, 416. pmid: 24288217
[9]	(a) Ma, W.; Weng, Z.; Fang, X.; Gu, L.; Song, Y.; Ackermann, L. Eur. J. Org. Chem. 2019, 2019, 41. pmid: 28429594
	(b) Ma, W.; Weng, Z.; Rogge, T.; Gu, Li.; Lin, J.; Peng, A.; Luo, X.; Gou, X.; Ackermann, L. Adv. Synth. Catal. 2018, 360, 704. pmid: 28429594
	(c) Mandal, A.; Dana, S.; Sahoo, H.; Grandhi, G. S.; Baidya, M. Org. Lett. 2017, 19, 2430. pmid: 28429594
	(d) Ma, W.; Dong, H.; Wang, D.; Ackermann, L. Adv. Synth. Catal. 2017, 359, 966. doi: 10.1002/adsc.201600937 pmid: 28429594
[10]	(a) Gao, F.; Zhu, W.; Zhang, D.-Y.; Li, S.-J.; Wang, J.; Liu, H. J. Org. Chem. 2016, 81, 9122. pmid: 25822847
	(b) Yan, S.-Y.; Liu, Y.-J.; Liu, B.; Liu, Y.-H.; Shi, B.-F. Chem. Commun. 2015, 51, 4069. pmid: 25822847
	(c) Yan, S.-Y.; Liu, Y.-J.; Liu, B.; Liu, Y.-H.; Zhang, Z.-Z.; Shi, B.-F. Chem. Commun. 2015, 51, 7341. pmid: 25822847
	(d) Lin, C.; Yu, W.-L.; Yao, J.-Z.; Wang, B.-J.; Liu, Z.-X.; Zhang, Y.-H. Org. Lett. 2015, 17, 1340. pmid: 25822847
	(e) Wang, X.; Qiu, R.-H.; Yan, C.-Y.; Reddy, V. P.; Zhu, L.-Z.; Xu, X.-H.; Yin, S.-F. Org. Lett. 2015, 17, 1970. pmid: 25822847
[11]	Chen, X.; Hao, X.-S.; Goodhue, C. E.; Yu, J.-Q. J. Am. Chem. Soc. 2006, 128, 6790. pmid: 16719450
[12]	Chu, L.-L.; Yue, X.-Y.; Qing, F.-L. Org. Lett. 2010, 12, 1644. pmid: 20222689
[13]	Tran, L. D.; Popov, I.; Daugulis, O. J. Am. Chem. Soc. 2012, 134, 18237. doi: 10.1021/ja3092278 pmid: 23102009
[14]	Liu, S.-L.; Li, X.-H.; Shi, T.-H.; Yang, G.-C.; Wang, H.-L.; Gong, J.-F.; Song, M.- P. Eur. J. Org. Chem. 2017, 2017, 2280.
[15]	(a) Li, Y.; Liu, Y.-J.; Shi, B.-F. Adv. Synth. Catal. 2017, 359, 4117. pmid: 25325568
	(b) Rao, W.-H.; Shi, B.-F. Org. Lett. 2015, 17, 2784. pmid: 25325568
	(c) Chen, F.-J.; Liao, G.; Li, X.; Wu, J.; Shi, B.-F. Org. Lett. 2014, 16, 5644. pmid: 25325568
[16]	(a) Jiang, Y.; Feng, Y.-Y.; Zou, J.-X.; Lei, S.; Hu, X.-L.; Yin, G.-F.; Tan, W.; Wang, Z. J. Org. Chem. 2019, 84, 10490. pmid: 31333031
	(b) Kong, W.-J.; Shao, Q.; Li, M.-H.; Zhou, Z.-L.; Xu, H.; Dai, H.-X.; Yu, J.-Q. Organometallics 2018, 37, 2832. doi: 10.1021/acs.organomet.8b00457 pmid: 31333031
	(c) Yan, X.-B.; Gao, P.; Yang, H.-B.; Li, Y.-X.; Liu, X.-Y.; Liang, Y.-M. Tetrahedron 2014, 70, 8730. pmid: 31333031
[17]	(a) Wang, T.; Xu, K.; Zhang, A.; Wang, W.; Liu, L. Chin. J. Org. Chem. 2018, 38, 259. (in Chinese)
	(王涛, 许凯, 张安安, 王万里, 刘澜涛, 有机化学, 2018, 38, 259.)
	(b) Wang, T.; Xu, K.; Liu, L.; Xie, H.; Li, Y.; Zhao, W-. X. Transition Met. Chem. 2016, 41, 525.
[18]	Ouyang, K.; Xi, Z. Acta Chim. Sinica 2013, 71, 13. (in Chinese)
	(欧阳昆冰, 席振峰, 化学学报, 2013, 71, 13.)
[19]	Shang, M.; Sun, S.-Z.; Dai, H.-X.; Yu, J.-Q. J. Am. Chem. Soc. 2014, 136, 3354. pmid: 24527701

醋酸铜促进的酰胺-噁唑啉化合物与芳基硫醇的C—H键双硫代化反应研究

Cu(OAc)₂-Mediated C—H Bond Dithiolation of Amide-Oxazolines with Aryl Thiols

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 7

References 19

Related Articles 15

Recommended Articles

Metrics

Comments

Entry	Reagent	Base	Temp./℃	Yield^b/%
1	Cu(OAc)₂	NaOAc	100	84
2	Cu(OAc)₂	KOAc	100	20
3	Cu(OAc)₂	CsOAc	100	30
4	Cu(OAc)₂	K₂CO₃	100	24
5	Cu(OAc)₂	Na₂CO₃	100	8
6	Cu(OAc)₂	Cs₂CO₃	100	Trace
7	Cu(OAc)₂	NaHCO₃	100	26
8	Cu(OAc)₂	K₃PO₄	100	15
9	Cu(OAc)₂	NaOAc	120	76
10	Cu(OAc)₂	NaOAc	80	90
11	Cu(OAc)₂	NaOAc	60	59
12	Cu(OAc)₂?H₂O	NaOAc	80	82
13	Co(OAc)₂	NaOAc	80	—
14	Cu(OAc)₂?4H₂O	NaOAc	80	—
15^c	Cu(OAc)₂	NaOAc	80	30
16^d	Cu(OAc)₂	NaOAc	80	73

[1]	Xiaoyang Gao, Ruirui Zhai, Xun Chen, Shuojin Wang. Recent Progress in C—H Bond Activation Reaction with Vinylene Carbonate [J]. Chinese Journal of Organic Chemistry, 2023, 43(9): 3119-3134.
[2]	Xiao Song, Jing Qing, Jun Li, Xuelei Jia, Fusong Wu, Junrong Huang, Jian Jin, Hengzhi You. Copper-Catalyzed Asymmetric Allyl Alkylation Using Grignard Reagents under Continuous Flow [J]. Chinese Journal of Organic Chemistry, 2023, 43(9): 3174-3179.
[3]	Zhongrong Xu, Jieping Wan, Yunyun Liu. Transition Metal-Free C—H Thiocyanation and Selenocyanation Based on Thermochemical, Photocatalytic and Electrochemical Process [J]. Chinese Journal of Organic Chemistry, 2023, 43(7): 2425-2446.
[4]	Fen Huang, Weiwei Luo, Jun Zhou. Research Progress of Polychloroalkylation Based on C—H Bond Cleavage [J]. Chinese Journal of Organic Chemistry, 2023, 43(7): 2368-2390.
[5]	Xiaoyu Lu, Xiaomei Sun, Yaqing Niu, Junchao Wang, Wenjing Yin, Mengting Gao, Zi Liu, Zhenghuan Wei, Tinghua Tao. Copper-Catalyzed Decarboxylative Cross-Coupling of α‑Fluoroacrylic Acids with N-Tosyl Oxaziridines [J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 2110-2119.
[6]	Zhicheng Bao, Muyao Li, Jianbo Wang. Copper-Catalyzed Cross-Coupling of Aryldiazoacetates with Bis[(pinacolato)boryl]methane [J]. Chinese Journal of Organic Chemistry, 2023, 43(5): 1808-1814.
[7]	Chunsheng Li, Xiaoqi Lian, Lianfen Chen. Copper-Catalyzed [4＋2] Annulations of Sulfoxonium Ylides and o-Phenylenediamines [J]. Chinese Journal of Organic Chemistry, 2023, 43(4): 1492-1498.
[8]	Yang Liu, Xiang Huang, Min Wang, Jian Liao. Enantioselective Copper-Catalyzed Mannich-Type Reaction of Cycic Ketimines and β,γ-Unsaturated N-Acylpyrazoles [J]. Chinese Journal of Organic Chemistry, 2023, 43(4): 1499-1509.
[9]	Chunyang Liu, Yan Li, Qian Zhang. Copper-Catalyzed Allylic C(sp³)—H Sulfonylation of Cyclic Olefins [J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 1091-1101.
[10]	Kongchuan Wu, Kaihong Lu, Jianbin Lin, Huijun Zhang. Research Progress in Ortho-C—H Bond Functionalization of Rylene Diimides [J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 1000-1011.
[11]	Yannian Pan, Xiao Qin, Chengkai Yuan, Yi Lu. Application of Ligands in Cp*Rh(III)-Catalyzed C—H Bond Functionalization Reaction [J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 924-948.
[12]	Biao Han, Weishuang Li, Shuhan Chen, Zelang Zhang, Xue Zhao, Yaoyao Zhang, Lei Zhu. Recent Advances in Copper-Catalyzed Silyl Addition of Unsaturated Compounds [J]. Chinese Journal of Organic Chemistry, 2023, 43(2): 555-572.
[13]	Yasir Mumtaz, Jie Liu, Xin Huang. Copper-Promoted Trifluoromethylthiolation of Anilines with CF₃SO₂Na [J]. Chinese Journal of Organic Chemistry, 2023, 43(2): 679-685.
[14]	Fang Wang, Lei Wang. Recent Advances in Functionalization of Aromatic C(sp²)—H Bonds Based on N-Nitroso Direction [J]. Chinese Journal of Organic Chemistry, 2023, 43(12): 4157-4167.
[15]	Meijiao Sun, Jing Tan, Yu Tan, Jinsong Peng, Chunxia Chen. Pd-Catalyzed C(2)—H Arylation of 3-(2-Aminopyrimidin-4-yl)indoles [J]. Chinese Journal of Organic Chemistry, 2023, 43(11): 3945-3959.