Citation: WANG Qingbing, GUO Zhengwei, CHEN Gong, HE Gang. DPPF-Mediated C―H Arylation of Arenes with Aryl Iodides for Synthesis of Biaryl Linkages[J]. Acta Physico-Chimica Sinica, ;2019, 35(9): 1021-1026. doi: 10.3866/PKU.WHXB201811044 shu

DPPF-Mediated C―H Arylation of Arenes with Aryl Iodides for Synthesis of Biaryl Linkages

State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, P. R. China

Corresponding author: CHEN Gong, gongchen@nankai.edu.cn HE Gang, hegang@nankai.edu.cn
Received Date: 30 November 2018
Revised Date: 12 January 2019
Accepted Date: 22 January 2019
Available Online: 24 September 2019
Fund Project: The project was supported by the National Natural Science Foundation of China 21672105Natural Science Foundation of Tianjin, China 18JCZDJC32800The project was supported by the National Natural Science Foundation of China 91753124The project was supported by the National Natural Science Foundation of China (21672105, 21725204, 91753124) and Natural Science Foundation of Tianjin, China (17JCYBJC19700, 18JCZDJC32800)Natural Science Foundation of Tianjin, China 17JCYBJC19700The project was supported by the National Natural Science Foundation of China 21725204

The broad existence of the biaryl linkage in bioactive organic molecules and functional materials makes it an attractive synthesis target via construction of aryl-aryl carbon bonds. Transition metal catalyzed cross-coupling reactions of two pre-functionalized aryl partners, e.g., Suzuki-Miyaura cross-coupling and Negishi cross-coupling reactions, are the main methods typically used for the construction of biaryl linkages. Since the end of the last century, transition metal catalyzed direct C-H arylation of unactivated arenes has emerged as a practical alternative to the well-established cross-coupling strategies. However, the use of transition metal catalysts and/or organometallic reagents would lead to problems, such as the disposal of waste from large-scale syntheses and the removal of heavy metal contaminants from pharmaceutical intermediates. In this regard, the base-promoted homolytic aromatic substitution (BHAS) reaction of aryl halides with unactivated arenes offers a simpler strategy for the synthesis of biaryl scaffolds, and avoids the use of transition metals. Although the BHAS reaction can proceed to a small extent without any additives, particularly at elevated temperatures, the addition of organic promoters would significantly accelerate the reaction rate and improve the overall efficiency of the process. Over the past ten years, a wide variety of N- and O-based organic promoters have been developed to promote the BHAS reaction in the presence of the tert-butoxide base. The mechanism of the BHAS reaction has been studied extensively, and is accepted as occurring via a radical chain process involving an aryl radical. However, the role and mode of initiation of most organic promoters studied remain controversial. The development of more and varied organic promoters will surely promote the mechanistic understanding and further development of the BHAS reaction. Herein, we report that 1, 1'-bis(diphenylphosphino)ferrocene (dppf, or DPPF) can act as a P-based promoter to facilitate the direct arylation of unactivated arenes with aryl iodides using potassium tert-butoxide as the base and electron donor. A broad range of aryl iodides and arenes reacted smoothly under the optimized reaction conditions, giving arylated products in good yields and with high regio-selectivity. Intramolecular C-H arylation also worked well following a sequence of single electron transfer (SET)/initiation, 5-exo-trig aryl radical addition, ring expansion, deprotonation, and re-aromatization/propagation. A mechanistic study indicated that the diphenylphosphino group of dppf played a vital role in the initiation step by enhancing the SET-inhibiting ability of the tert-butoxide anion. A primary kinetic isotope effect was observed in the parallel reactions between 4-methoxy-iodobenzene with benzene and deuterated benzene, implying that the deprotonation of the cyclohexadienyl radical intermediate by tert-butoxide was the rate-determining step in the radical chain pathway.
- C―H arylation,
- tert-butoxide,
- DPPF,
- Radical,
- Biaryl synthesis
1. [1]
  Bringmann, G.; Walter, R.; Weirich, R. Angew. Chem. Int. Edit. 1990, 29, 977. doi: 10.1002/anie.199009771 doi: 10.1002/anie.199009771
2. [2]
  Zhang, Y. -F.; Shi, Z. -J. Acc. Chem. Res. 2018, 52, 161. doi: 10.1021/acs.accounts.8b00408 doi: 10.1021/acs.accounts.8b00408
3. [3]
  Lei, A.; Liu, W.; Liu, C.; Chen, M. Dalton Trans. 2010, 39, 10352. doi: 10.1039/c0dt00486c doi: 10.1039/c0dt00486c
4. [4]
  Ackermann, L.; Vicente, R.; Kapdi, A. R. Angew. Chem. Int. Edit. 2009, 48, 9792. doi: 10.1002/anie.200902996 doi: 10.1002/anie.200902996
5. [5]
  Bolton, R.; Williams, G. H. Chem. Soc. Rev. 1986, 15, 261. doi: 10.1039/cs9861500261 doi: 10.1039/cs9861500261
6. [6]
  Bowman, W. R.; Storey, J. M. Chem. Soc. Rev. 2007, 36, 1803. doi: 10.1039/b605183a doi: 10.1039/b605183a
7. [7]
  Yanagisawa, S.; Ueda, K.; Taniguchi, T.; Itami, K. Org. Lett. 2008, 10, 4673. doi: 10.1021/ol8019764 doi: 10.1021/ol8019764
8. [8]
  Liu, W.; Cao, H.; Zhang, H.; Zhang, H.; Chung, K. H.; He, C.; Wang, H.; Kwong, F. Y.; Lei, A. J. Am. Chem. Soc. 2010, 132, 16737. doi: 10.1021/ja103050x doi: 10.1021/ja103050x
9. [9]
  Sun, C. -L.; Li, H.; Yu, D. -G.; Yu, M.; Zhou, X.; Lu, X. -Y.; Huang, K.; Zheng, S. -F.; Li, B. -J.; Shi, Z. -J. Nat. Chem. 2010, 2, 1044. doi: 10.1038/NCHEM.862 doi: 10.1038/NCHEM.862
10. [10]
  Shirakawa, E.; Itoh, K. -I.; Higashino, T.; Hayashi, T. J. Am. Chem. Soc. 2010, 132, 15537. doi: 10.1021/ja1080822 doi: 10.1021/ja1080822
11. [11]
  Leadbeater, N. E. Nat. Chem. 2010, 2, 1007. doi: 10.1038/ NCHEM.913 doi: 10.1038/NCHEM.913
12. [12]
  Studer, A.; Curran, D. P. Angew. Chem. Int. Edit. 2011, 50, 5018. doi: 10.1002/anie.201101597 doi: 10.1002/anie.201101597
13. [13]
  Pan, S. C. Beilstein J. Org. Chem. 2012, 8, 1374. doi: 10.3762/bjoc.8.159 doi: 10.3762/bjoc.8.159
14. [14]
  Chan, T. L.; Wu, Y.; Choy, P. Y.; Kwong, F. Y. Chem. -Eur. J. 2013, 19, 15802. doi: 10.1002/chem.201301583 doi: 10.1002/chem.201301583
15. [15]
  Sun, C. -L.; Shi, Z. -J. Chem. Rev. 2014, 114, 9219. doi: 10.1021/cr400274j doi: 10.1021/cr400274j
16. [16]
  Hofmann, J.; Heinrich, M. R. Tetrahedron Lett. 2016, 57, 4334. doi: 10.1016/j.tetlet.2016.08.034 doi: 10.1016/j.tetlet.2016.08.034
17. [17]
  Qiu, Y.; Liu, Y.; Yang, K.; Hong, W.; Li, Z.; Wang, Z.; Yao, Z.; Jiang, S. Org. Lett. 2011, 13, 3556. doi: 10.1021/ol2009208 doi: 10.1021/ol2009208
18. [18]
  Liu, H.; Yin, B.; Gao, Z.; Li, Y.; Jiang, H. Chem. Commun. 2012, 48, 2033. doi: 10.1039/c2cc16790e doi: 10.1039/c2cc16790e
19. [19]
  Ng, Y. S.; Chan, C. S.; Chan, K. S. Tetrahedron Lett. 2012, 53, 3911. doi: 10.1016/j.tetlet.2012.05.073 doi: 10.1016/j.tetlet.2012.05.073
20. [20]
  Tanimoro, K.; Ueno, M.; Takeda, K.; Kirihata, M.; Tanimori, S. J. Org. Chem. 2012, 77, 7844. doi: 10.1021/jo3008594 doi: 10.1021/jo3008594
21. [21]
  Chen, W. -C.; Hsu, Y. -C.; Shih, W. -C.; Lee, C. -Y.; Chuang, W. -H.; Tsai, Y. -F.; Chen, P. P. -Y.; Ong, T. -G. Chem. Commun. 2012, 48, 6702. doi: 10.1039/c2cc32519e doi: 10.1039/c2cc32519e
22. [22]
  Sharma, S.; Kumar, M.; Kumar, V.; Kumar, N. Tetrahedron Lett. 2013, 54, 4868. doi: 10.1016/j.tetlet.2013.06.125 doi: 10.1016/j.tetlet.2013.06.125
23. [23]
  Liu, W.; Tian, F.; Wang, X.; Yu, H.; Bi, Y. Chem. Commun. 2013, 49, 2983. doi: 10.1039/c3cc40695d doi: 10.1039/c3cc40695d
24. [24]
  Zhao, H.; Shen, J.; Guo, J.; Ye, R.; Zeng, H. Chem. Commun. 2013, 49, 2323. doi: 10.1039/c3cc00019b doi: 10.1039/c3cc00019b
25. [25]
  Song, Q.; Zhang, D.; Zhu, Q.; Xu, Y. Org. Lett. 2014, 16, 5272. doi: 10.1021/ol502370r doi: 10.1021/ol502370r
26. [26]
  Cuthbertson, J.; Gray, V. J.; Wilden, J. D. Chem. Commun. 2014, 50, 2575. doi: 10.1039/c3cc49019j doi: 10.1039/c3cc49019j
27. [27]
  Wu, Y.; Choy, P. Y.; Kwong, F. Y. Org. Biomol. Chem. 2014, 12, 6820. doi: 10.1039/c4ob01211a doi: 10.1039/c4ob01211a
28. [28]
  Yi, H.; Jutand, A.; Lei, A. Chem. Commun. 2015, 51, 545. doi: 10.1039/c4cc07299e doi: 10.1039/c4cc07299e
29. [29]
  Zhou, S.; Anderson, G. M.; Mondal, B.; Doni, E.; Ironmonger, V.; Kranz, M.; Tuttle, T.; Murphy, J. A. Chem. Sci. 2014, 5, 476. doi: 10.1039/c3sc52315b doi: 10.1039/c3sc52315b
30. [30]
  Zhou, S.; Doni, E.; Anderson, G. M.; Kane, R. G.; MacDougall, S. W.; Ironmonger, V. M.; Tuttle, T.; Murphy, J. A. J. Am. Chem. Soc. 2014, 136, 17818. doi: 10.1021/ja5101036 doi: 10.1021/ja5101036
31. [31]
  Barham, J. P.; Coulthard, G.; Emery, K. J.; Doni, E.; Cumine, F.; Nocera, G.; John, M. P.; Berlouis, L. E. A.; McGuire, T.; Tuttle, T.; et al. J. Am. Chem. Soc. 2016, 138, 7402. doi: 10.1021/jacs.6b03282 doi: 10.1021/jacs.6b03282
32. [32]
  Gao, Y.; Tang, P.; Zhou, H.; Zhang, W.; Yang, H.; Yan, N.; Hu, G.; Mei, D.; Wang, J.; Ma, D. Angew. Chem. Int. Edit. 2016, 55, 3124. doi: 10.1002/anie.201510081 doi: 10.1002/anie.201510081
33. [33]
  Paira, R.; Singh, B.; Hota, P. K.; Ahmed, J.; Sau, S. C.; Johnpeter, J. P.; Mandal, S. K. J. Org. Chem. 2016, 81, 2432. doi: 10.1021/acs.joc.6b00002 doi: 10.1021/acs.joc.6b00002
34. [34]
  Zhang, L.; Yang, H.; Jiao, L. J. Am. Chem. Soc. 2016, 138, 7151. doi: 10.1021/jacs.6b03442 doi: 10.1021/jacs.6b03442
35. [35]
  Yang, H.; Chu, D. -Z.; Jiao, L. Chem. Sci. 2018, 9, 1534. doi: 10.1039/c7sc04450j doi: 10.1039/c7sc04450j
36. [36]
  Guo, Z. W.; Li, M.; Mou, X. Q.; He, G.; Xue, X. S.; Chen, G. Org. Lett. 2018, 20, 1684. doi: 10.1021/acs.orglett.8b00530 doi: 10.1021/acs.orglett.8b00530
37. [37]
  Hou, L.; Zhou, Z.; Wang, D.; Zhang, Y.; Chen, X.; Zhou, L.; Hong, Y.; Liu, W.; Hou, Y.; Tong, X. Org. Lett. 2017, 19, 6328. doi: 10.1021/acs.orglett.7b03135 doi: 10.1021/acs.orglett.7b03135
38. [38]
  Studer, A.; Curran, D. P. Nat. Chem. 2014, 6, 765. doi: 10.1038/NCHEM.2031 doi: 10.1038/NCHEM.2031
39. [39]
  Hofmann, J.; Clark, T.; Heinrich, M. R. J. Org. Chem. 2016, 81, 9785. doi: 10.1021/acs.joc.6b01840 doi: 10.1021/acs.joc.6b01840
40. [40]
  Roman, D. S.; Takahashi, Y.; Charette, A. B. Org. Lett. 2011, 13, 3242. doi: 10.1021/ol201160s doi: 10.1021/ol201160s
41. [41]
  Sun, C. -L.; Gu, Y. -F.; Huang, W. -P.; Shi, Z. -J. Chem. Commun. 2011, 47, 9813. doi: 10.1039/c1cc13907j doi: 10.1039/c1cc13907j
42. [42]
  Bhakuni, B. S.; Kumar, A.; Balkrishna, S. J.; Sheikh, J. A.; Konar, S.; Kumar, S. Org. Lett. 2012, 14, 2838. doi: 10.1021/ol301077y doi: 10.1021/ol301077y
43. [43]
  Wu, Y.; Wong, S. M.; Mao, F.; Chan, T. L.; Kwong, F. Y. Org. Lett. 2012, 14, 5306. doi: 10.1021/ol302489n doi: 10.1021/ol302489n
44. [44]
  De, S.; Ghosh, S.; Bhunia, S.; Sheikh, J. A.; Bisai, A. Org. Lett. 2012, 14, 4466. doi: 10.1021/ol3019677 doi: 10.1021/ol3019677
45. [45]
  Simmons, E. M.; Hartwig, J. F. Angew. Chem. Int. Edit. 2012, 51, 3066. doi: 10.1002/anie.201107334 doi: 10.1002/anie.201107334
1. [1]
  Zhengzhong Zhu , Shaojun Hu , Zhi Liu , Lipeng Zhou , Chongbin Tian , Qingfu Sun . A cationic radical lanthanide organic tetrahedron with remarkable coordination enhanced radical stability. Chinese Chemical Letters, 2025, 36(2): 109641-. doi: 10.1016/j.cclet.2024.109641
2. [2]
  Xiao-Bo Liu , Ren-Ming Liu , Xiao-Di Bao , Hua-Jian Xu , Qi Zhang , Yu-Feng Liang . Nickel-catalyzed reductive formylation of aryl halides via formyl radical. Chinese Chemical Letters, 2024, 35(12): 109783-. doi: 10.1016/j.cclet.2024.109783
3. [3]
  Le Zhang , Hui-Yu Xie , Xin Li , Li-Ying Sun , Ying-Feng Han . SOMO-HOMO level conversion in triarylmethyl-cored N-heterocyclic carbene-Au(I) complexes triggered by selecting coordination halogens. Chinese Chemical Letters, 2024, 35(11): 109465-. doi: 10.1016/j.cclet.2023.109465
4. [4]
  Huaixiang Yang , Miao-Miao Li , Aijun Zhang , Jiefei Guo , Yongqi Yu , Wei Ding . Visible-light-induced photocatalyst- and metal-free radical phosphinoyloximation of alkenes with tert-butyl nitrite as bifunctional reagent. Chinese Chemical Letters, 2025, 36(3): 110425-. doi: 10.1016/j.cclet.2024.110425
5. [5]
  Haoran Shi , Jiaxin Wang , Yuqin Zhu , Hongyang Li , Guodong Ju , Lanlan Zhang , Chao Wang . Highly selective α-C(sp³)-H arylation of alkenyl amides via nickel chain-walking catalysis. Chinese Chemical Letters, 2024, 35(7): 109333-. doi: 10.1016/j.cclet.2023.109333
6. [6]
  Lei Shi . Nucleophilicity and Electrophilicity of Radicals. University Chemistry, 2024, 39(11): 131-135. doi: 10.3866/PKU.DXHX202402018
7. [7]
  Wei Zhou , Xi Chen , Lin Lu , Xian-Rong Song , Mu-Jia Luo , Qiang Xiao . Recent advances in electrocatalytic generation of indole-derived radical cations and their applications in organic synthesis. Chinese Chemical Letters, 2024, 35(4): 108902-. doi: 10.1016/j.cclet.2023.108902
8. [8]
  Xiaoling WANG , Hongwu ZHANG , Daofu LIU . Synthesis, structure, and magnetic property of a cobalt(Ⅱ) complex based on pyridyl-substituted imino nitroxide radical. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 407-412. doi: 10.11862/CJIC.20240214
9. [9]
  Qi Li , Zi-Lu Wang , Yun-He Xu . Copper-catalyzed 1,4-silylcyanation of 1,3-enynes: A silyl radical-initiated approach for synthesis of difunctionalized allenes. Chinese Chemical Letters, 2025, 36(3): 109991-. doi: 10.1016/j.cclet.2024.109991
10. [10]
  Shulei Hu , Yu Zhang , Xiong Xie , Luhan Li , Kaixian Chen , Hong Liu , Jiang Wang . Rh(Ⅲ)-catalyzed late-stage C-H alkenylation and macrolactamization for the synthesis of cyclic peptides with unique Trp(C7)-alkene crosslinks. Chinese Chemical Letters, 2024, 35(8): 109408-. doi: 10.1016/j.cclet.2023.109408
11. [11]
  Jingping Hu , Jing Xu . Total synthesis of a putative yuzurimine-type Daphniphyllum alkaloid C₁₄–epi-deoxycalyciphylline H. Chinese Chemical Letters, 2024, 35(4): 108733-. doi: 10.1016/j.cclet.2023.108733
12. [12]
  Peng Wang , Jianjun Wang , Ni Song , Xin Zhou , Ming Li . Radical dehydroxymethylative fluorination of aliphatic primary alcohols and diverse functionalization of α-fluoroimides via BF₃·OEt₂-catalyzed C‒F bond activation. Chinese Chemical Letters, 2025, 36(1): 109748-. doi: 10.1016/j.cclet.2024.109748
13. [13]
  Peng ZHOU , Xiao CAI , Qingxiang MA , Xu LIU . Effects of Cu doping on the structure and optical properties of Au₁₁(dppf)₄Cl₂ nanocluster. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1254-1260. doi: 10.11862/CJIC.20240047
14. [14]
  Tao Zhou , Jing Zhou , Yunyun Liu , Jie-Ping Wan , Fen-Er Chen . Transition metal-free tunable synthesis of 3-(trifluoromethylthio) and 3-trifluoromethylsulfinyl chromones via domino C–H functionalization and chromone annulation of enaminones. Chinese Chemical Letters, 2024, 35(11): 109683-. doi: 10.1016/j.cclet.2024.109683
15. [15]
  Jindian Duan , Xiaojuan Ding , Pui Ying Choy , Binyan Xu , Luchao Li , Hong Qin , Zheng Fang , Fuk Yee Kwong , Kai Guo . Oxidative spirolactonisation for modular access of γ-spirolactones via a radical tandem annulation pathway. Chinese Chemical Letters, 2024, 35(10): 109565-. doi: 10.1016/j.cclet.2024.109565
16. [16]
  Jing-Qi Tao , Shuai Liu , Tian-Yu Zhang , Hong Xin , Xu Yang , Xin-Hua Duan , Li-Na Guo . Photoinduced copper-catalyzed alkoxyl radical-triggered ring-expansion/aminocarbonylation cascade. Chinese Chemical Letters, 2024, 35(6): 109263-. doi: 10.1016/j.cclet.2023.109263
17. [17]
  Yu-Yu Tan , Lin-Heng He , Wei-Min He . Copper-mediated assembly of SO₂F group via radical fluorine-atom transfer strategy. Chinese Chemical Letters, 2024, 35(9): 109986-. doi: 10.1016/j.cclet.2024.109986
18. [18]
  Yuhan Liu , Jingyang Zhang , Gongming Yang , Jian Wang . Highly enantioselective carbene-catalyzed δ-lactonization via radical relay cross-coupling. Chinese Chemical Letters, 2025, 36(1): 109790-. doi: 10.1016/j.cclet.2024.109790
19. [19]
  Yaxuan Jin , Chao Zhang , Guigang Zhang . Atomically dispersed low-valent Au on poly(heptazine imide) boosts photocatalytic hydroxyl radical production. Chinese Journal of Structural Chemistry, 2024, 43(12): 100414-100414. doi: 10.1016/j.cjsc.2024.100414
20. [20]
  Shengkai Li , Yuqin Zou , Chen Chen , Shuangyin Wang , Zhao-Qing Liu . Defect engineered electrocatalysts for C–N coupling reactions toward urea synthesis. Chinese Chemical Letters, 2024, 35(8): 109147-. doi: 10.1016/j.cclet.2023.109147

Get Citation

PDF

XML

Metrics

PDF Downloads(9)
Abstract views(763)
HTML views(21)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142