Photoinduced Nickel-Catalyzed Reductive Heck Reaction

doi:10.6023/cjoc202408039

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (5): 1691-1697.DOI: 10.6023/cjoc202408039 Previous Articles Next Articles

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可见光诱导镍催化烯烃还原Heck反应

刘俊杰^†, 赵红平^†, 胡媛媛, 汪恒昕, 袁伟明^*()

华中科技大学化学与化工学院武汉 430074

收稿日期:2024-08-31 修回日期:2024-10-09 发布日期:2024-11-27
作者简介:
^†共同第一作者.
基金资助:
国家自然科学基金(22201087)

Photoinduced Nickel-Catalyzed Reductive Heck Reaction

Junjie Liu^†, Hongping Zhao^†, Yuanyuan Hu, Hengxin Wang, Weiming Yuan^*()

School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074

Received:2024-08-31 Revised:2024-10-09 Published:2024-11-27
Contact: * E-mail: yuanwm@hust.edu.cn
About author:
^†The authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22201087)

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Abstract

An efficient visible-light induced nickel-catalyzed reductive Heck reaction of alkenes by using mild organic reductant Hantzsch ester (HEH) instead of traditional metal reductants or hydride reagents was developed. The reductive hydroarylation of acrylates with aryl halides was successfully achieved without requiring exogenous photoredox catalysts. This reaction is highlighted by the simple and mild conditions, good functional group tolerance, thus providing a complementary approach for alkenes reductive Heck reaction.

Key words: nickel, reductive Heck reaction, visible light, organic reductant, alkene

Cite this article

Junjie Liu, Hongping Zhao, Yuanyuan Hu, Hengxin Wang, Weiming Yuan. Photoinduced Nickel-Catalyzed Reductive Heck Reaction[J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1691-1697.

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Fig. & Tab. 7

Scheme 1. Ni-Catalyzed reductive Heck reaction

Entry	Deviation from the standard condition	Yield^b/%
1	None	78
2	NiBr₂	22
3	Ni(cod)₂	65
4	L2	Trace
5	L3	16
6	L4	30
7	DMF	57
8	DMSO	24
9	THF	Trace
10	456 nm blue LED	0
11	No Ni, ligand, HEH, base, or light	0

Table 1. Optimization of the reaction conditionsa

Table 2. Substrate scope of alkenesa

Table 3. Substrate scope of aryl halidesa

Scheme 2. D2O quenching experiment and BHT trapping experiment

Figure 1. Stern-Volmer quenching experiment

Scheme 3. Proposed mechanism

References 12

[1]	Xie J.-Q.; Liang R.-X.; Jia Y.-X. Chin. J. Chem. 2021, 39, 710.
[2]	(a) Minatti A.; Zheng X.; Buchwald S. L. J. Org. Chem. 2007, 72, 9253. pmid: 17967034
	(b) Shen C.; Liu R.-R.; Fan R.-J.; Li Y.-L.; Xu T.-F.; Gao J.-R.; Jia Y.-X. J. Am. Chem. Soc. 2015, 137, 4936. pmid: 17967034
	(c) Kong W.; Wang Q.; Zhu J. Angew. Chem., Int. Ed. 2017, 56, 3987. pmid: 17967034
	(d) Zhang Z.-M.; Xu B.; Qian Y.; Wu L.; Wu Y.; Zhou L.; Liu Y.; Zhang J. Angew. Chem., Int. Ed. 2018, 57, 10373. pmid: 17967034
	(e) Yuan Z.; Feng Z.; Zeng Y.; Zhao X.; Lin A.; Yao H. Angew. Chem., Int. Ed. 2019, 58, 2884. pmid: 17967034
	(f) Huang X.; Nguyen M. H.; Pu M.; Zhang L.; Chi Y. R.; Wu Y.-D.; Zhou J. S. Angew. Chem., Int. Ed. 2020, 59, 10814. pmid: 17967034
	(g) Liu S.; Zhou J. S. Chem. Commun. 2013, 49, 11758. pmid: 17967034
	(h) Yue G.; Lei K.; Hirao H.; Zhou J. S. Angew. Chem., Int. Ed. 2015, 54, 6531. pmid: 17967034
	(i) Jang J. Y.; Larin E. M.; Lautens M. Angew. Chem., Int. Ed. 2017, 56, 11927. pmid: 17967034
	(j) Mannathan S.; Raoufmoghaddam S.; Reek J. N. H.; de Vries J. G.; Minnaard A. J. ChemCatChem 2017, 9, 551. pmid: 17967034
	(k) Liang R.-X.; Yang R.-Z.; Liu R.-R.; Jia Y.-X. Org. Chem. Front. 2018, 5, 1840. pmid: 17967034
	(l) Hou L.; Yuan Y.; Tong X. Org. Biomol. Chem. 2017, 15, 4803. pmid: 17967034
	(m) Oxtoby L. J.; Li Z. Q.; Tran V. T.; Erbay T. G.; Deng R.; Liu P.; Engle K. M. Angew. Chem., Int. Ed. 2020, 59, 8885. pmid: 17967034
	(n) Niu J.; Wu H.; Niu C.; Huang G.; Zhang C. ACS Catal. 2022, 12, 8667. pmid: 17967034
	(o) Shirai T.; Migitera Y.; Nakajima R.; Kumamoto T. J. Org. Chem. 2024, 89, 2787. pmid: 17967034
[3]	(a) Lin B.-L.; Liu L.; Fu Y.; Luo S.-W.; Chen Q.; Guo Q.-X. Organometallics 2004, 23, 2114.
	(b) Dürr A. B.; Yin G.; Kalvet I.; Napoly F.; Schoenebeck F. Chem. Sci. 2016, 7, 1076.
	(c) Li X.; Hong X. J. Organomet. Chem. 2018, 864, 68.
[4]	(a) Boldrini G. P.; Savoia D.; Tagliavini E.; Trombini C.; Ronchi A. U. J. Organomet. Chem. 1986, 301, C62.
	(b) Sustmann R.; Hopp P.; Holl P. Tetrahedron Lett. 1989, 30, 689.
	(c) Márquez I. R.; Miguel D.; Millán A.; Marcos M. L.; de Cienfuegos L. A.; Campaña A. G.; Cuerva J. M. J. Org. Chem. 2014, 79, 1529.
	(d) Shukla P.; Sharma A.; Pallavi B.; Cheng C. H. Tetrahedron 2015, 71, 2260.
[5]	(a) Kim H.; Lee C. Org. Lett. 2011, 13, 2050.
	(b) Qin X.; Lee M. W. Y.; Zhou J. S. Angew. Chem., Int. Ed. 2017, 56, 12723.
	(c) Qin X.; Yao Lee M. W.; Zhou J. S. Org. Lett. 2019, 21, 5990.
	(d) Yang F.; Jin Y.; Wang C. Org. Lett. 2019, 21, 6989.
[6]	Huang X.; Teng S.; Chi Y. R.; Xu W.; Pu M.; Wu Y.-D.; Zhou J. S. Angew. Chem. Int. Ed. 2021, 60, 2828.
[7]	Broggi J.; Terme T.; Vanelle P. Angew. Chem. Int. Ed. 2014, 53, 384. doi: 10.1002/anie.201209060 pmid: 24273111
[8]	(a) Duan Z.; Li W.; Lei A. Org. Lett. 2016, 18, 4012. pmid: 34168786
	(b) Zhang P.; Le C. C.; MacMillan D. W. C. J. Am. Chem. Soc. 2016, 138, 8084. pmid: 34168786
	(c) Yi J.; Badir S. O.; Kammer L. M.; Ribagorda M.; Molander G. A. Org. Lett. 2019, 21, 3346. pmid: 34168786
	(d) Parasram M.; Shields B. J.; Ahmad O.; Knauber T.; Doyle A. G. ACS Catal. 2020, 10, 5821. doi: 10.1021/acscatal.0c01199 pmid: 34168786
	(e) Guan H.; Zhang Q.; Walsh P. J.; Mao J. Angew. Chem., Int. Ed. 2020, 59, 5172. pmid: 34168786
	(f) Sun S.-Z.; Duan Y.; Mega R. S.; Somerville R. J.; Martin R. Angew. Chem., Int. Ed. 2020, 59, 4370. pmid: 34168786
	(g) Qian P.; Guan H.; Wang Y.-E.; Lu Q.; Zhang F.; Xiong D.; Walsh P. J.; Mao J. Nat. Commun. 2021, 12, 6613. pmid: 34168786
	(h) Kammer L. M.; Badir S. O.; Hu R.-M.; Molander G. A. Chem. Sci. 2021, 12, 5450. doi: 10.1039/d1sc00943e pmid: 34168786
	(i) Peng L.; Li Z.; Yin G. Org. Lett. 2018, 20, 1880. pmid: 34168786
[9]	(a) Xi X.; Luo Y.; Li W.; Xu M.; Zhao H.; Chen Y.; Zheng S.; Qi X.; Yuan W. Angew. Chem., Int. Ed. 2022, e202114731.
	(b) Xi X.; Chen Y.; Yuan W. Org. Lett. 2022, 24, 3938.
	(c) Chen Y.; Xi X.; Yuan W. Org. Chem. Front. 2023, 10, 3669.
	(d) Zhao H.; Yuan W. Chem. Sci. 2023, 14, 1485.
	(e) Liu J.; Chen Y.; Zhao H.; Yuan W. Org. Chem. Front. 2024, 11, 1205.
[10]	He X.-C.; Li K.-R.; Gao J.; Guan J.-P.; Chen H.-B.; Xiang H.-Y.; Chen K.; Yang H. Org. Lett. 2023, 25, 4056.
[11]	Jung J.; Kim J.; Park G.; You Y.; Cho E. J. Adv. Synth. Catal. 2016, 358, 74.
[12]	Zuo Z.; Ahneman D. T.; Chu L.; Terrett J. A.; Doyle A. G.; MacMillan D. W. C. Science 2014, 345, 437.

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可见光诱导镍催化烯烃还原Heck反应

Photoinduced Nickel-Catalyzed Reductive Heck Reaction

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Fig. & Tab. 7

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