Citation: Guan Honghao, Chen Lei, Liu Lei. Oxidative C—H Alkynylation of Unactivated Acyclic Ethers[J]. Acta Chimica Sinica, ;2018, 76(6): 440-444. doi: 10.6023/A18030083 shu

Oxidative C—H Alkynylation of Unactivated Acyclic Ethers

Guan Honghao ^a ,
Chen Lei ^b ,
Liu Lei ^a,b,,

a.
School of Pharmaceutical Science, Shandong University, Jinan 250012
b.
School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100

Corresponding author: Liu Lei, leiliu@sdu.edu.cn
Received Date: 1 March 2018
Available Online: 9 June 2018
Fund Project: Project supported by the National Natural Science Foundation of China (Nos. 21722204, 21472112) and Fok Ying Tung Education Foundation (No. 151035)the National Natural Science Foundation of China 21722204the National Natural Science Foundation of China 21472112Fok Ying Tung Education Foundation 151035

Figures(3)

C—C bond forming reactions through cross-dehydrogenative coupling (CDC) of two readily available C—H components under oxidative conditions have emerged as one of the most straightforward and economical approaches for increasing molecular complexity and functional group content with minimal waste generation. CDC reactions involving oxidative functionalization of sp³ C—H bonds of both cyclic and acyclic amines with diverse partners have been extensively explored. In sharp contrast, the CDC of corresponding ether substrates remains relatively underdeveloped. Current approaches predominantly focus on cyclic ethers as well as acyclic benzylic ethers. The CDC reaction of extensively existing unactivated acyclic ethers proved to be much more challenging, which might be ascribed to their inherent low reactivity. On the other hand, the existing protocols for unactivated ethers rely heavily on peroxide-mediated oxidation systems, which typically required high temperature and a large excess of ether substrates as the solvent. Accordingly, coupling partners that can be compatible with such harsh conditions are largely restricted to sp² or sp³ C—H reagents with relatively low manipulation capability, such as arenes, heteroarenes, and 1, 3-dicarbonyl moieties. Alkynes represent common structural motifs spread across the fields of biology, chemistry, material science, and medicine, and act as global handles for diverse functionalities. Therefore, the development of a mild approach for CDC of unactivated acyclic ethers with terminal alkynes is highly desired. In 2014, our group developed a mild Ph₃CCl/GaCl₃ mediated oxidation system, allowing to achieve the oxidative C—H alkynylation of tetrahydrofuran with organoboranes. Herein, we reported the first CDC of unactivated acyclic ethers with terminal alkynes promoted by Ph₃CCl/GaCl₃. The reaction proceeded at room temperature in CH₂Cl₂, thus avoiding the employment of excess ether as the solvent. The typical procedure is as follows:a mixture of unactivated acyclic ether (2.0 mmol), terminal alkyne (0.1 mmol), Ph₃CCl (0.1 mmol), and CuI (0.03 mmol) in CH₂Cl₂ at r.t. was added GaCl₃ (0.1 mmol) in a glove box to afford the expected coupling products in moderate to good yields. The Ph₃CCl/GaCl₃ mediated oxidative C—H alkynylation of unactivated acyclic ethers with alkyl substituted alkynylboranes was further established to overcome the relative low efficiency for the CDC reaction involving alkyl substituted terminal alkynes.
- acyclic ether,
- unactivated ether,
- terminal alkyne,
- cross-dehydrogenative coupling,
- carbocation
1. [1]
  (a) Godula, K. ; Sames, D. Science 2006, 312, 67; (b) Davies, H. M. L. Angew. Chem., Int. Ed. 2006, 45, 6422; (c) Gutekunst, W. R. ; Baran, P. S. Chem. Soc. Rev. 2011, 40, 1976; (d) Giri, R. ; Shi, B. F. ; Engle, K. M. ; Maugel, N. ; Yu, J. Q. Chem. Soc. Rev. 2009, 38, 3242.
2. [2]
3. [3]
  (a) Wender, P. A. ; Verma, V. A. ; Paxton, T. J. ; Pillow, T. H. Acc. Chem. Res. 2008, 41, 40; (b) Trost, B. M. Acc. Chem. Res. 2002, 35, 695.
4. [4]
  For cross-dehydrogenative coupling of amines, see: (a) Li, Z. ; Li, C. J. J. Am. Chem. Soc. 2004, 126, 11810; (b) Li, Z. ; Li, C. J. J. Am. Chem. Soc. 2005, 127, 3672; (c) Li, Z. ; Li, C. J. J. Am. Chem. Soc. 2005, 127, 6968; (d) Li, Z. ; Yu, R. ; Li, H. Angew. Chem., Int. Ed. 2008, 47, 7497; (e) Murahashi, S. I. ; Nakae, T. ; Terai, H. ; Komiya, N. J. Am. Chem. Soc. 2008, 130, 11005; (f) Yang, F. ; Li, J. ; Xie, J. ; Huang, Z. -Z. Org. Lett. 2010, 12, 5214; (g) Hari, D. P. ; König, B. Org. Lett. 2011, 13, 3852; (h) Boess, E. ; Sureshkumar, D. ; Sud, A. ; Wirtz, C. ; Farès, C. ; Klussmann, M. J. Am. Chem. Soc. 2011, 133, 8106; (i) Richter, H. ; García Mancheño, O. Eur. J. Org. Chem. 2010, 4460; (j) Meng, Q. -Y. ; Zhong, J. -J. ; Liu, Q. ; Gao, X. -W. ; Zhang, H. -H. ; Lei, T. ; Li, Z. -J. ; Feng, K. ; Chen, B. ; Tung, C. -H. ; Wu, L. -Z. J. Am. Chem. Soc. 2013, 135, 19052; (k) Liu, X. ; Sun, B. ; Xie, Z. ; Qin, X. ; Liu, L. ; Lou, H. J. Org. Chem. 2013, 78, 3104; (l) Xie, Z. ; Liu, L. ; Chen, W. ; Zheng, H. ; Xu, Q. ; Yuan, H. ; Lou, H. Angew. Chem., Int. Ed. 2014, 53, 3904; (m) Wu, C. -J. ; Zhong, J. -J. ; Meng, Q. -Y. ; Lei, T. ; Gao, X. -W. ; Tung, C. -H. ; Wu, L. -Z. Org. Lett. 2015, 17, 884; (n) Long, H. ; Wang, G. ; Lu, R. ; Xu, M. ; Zhang, K. ; Qi, S. ; He, Y. ; Bu, Y. ; Liu, L. Org. Lett. 2017, 19, 2146.
5. [5]
  For asymmetric cross-dehydrogenative coupling of amines, see: (a) Zhang, J. ; Tiwari, B. ; Xing, C. ; Chen, X. ; Chi, Y. R. Angew. Chem., Int. Ed. 2012, 51, 3649; (b) Zhang, G. ; Zhang, Y. ; Wang, R. ; Angew. Chem., Int. Ed. 2011, 50, 10429; (c) Zhang, G. ; Ma, Y. ; Wang, S. ; Kong, W. ; Wang, R. Chem. Sci. 2013, 4, 2645; (d) Neel, A. J. ; Hehn, J. P. ; Tripet, P. F. ; Toste, F. D. J. Am. Chem. Soc. 2013, 135, 14044; (e) Liu, X. ; Sun, S. ; Meng, Z. ; Lou, H. ; Liu, L. Org. Lett. 2015, 17, 2396; (f) Xie, Z. ; Liu, X. ; Liu, L. Org. Lett. 2016, 18, 2982; (g) Xie, Z. ; Zan, X. ; Sun, S. ; Pan, X. ; Liu, L. Org. Lett. 2016, 18, 3944; (h) Yang, Q. ; Zhang, L. ; Ye, C. ; Luo, S. ; Wu, L. -Z. ; Tung, C. -H. Angew. Chem., Int. Ed. 2017, 56, 3694; (i) Fu, N. ; Li, L. ; Yang, Q. ; Luo, S. Org. Lett. 2017, 19, 2122.
6. [6]
  For cross-dehydrogenative coupling of cyclic benzylic ethers, see: (a) Zhang, Y. H. ; Li, C. J. J. Am. Chem. Soc. 2006, 128, 4242; (b) Zhang, Y. H. ; Li, C. J. Angew. Chem., Int. Ed. 2006, 45, 1949; (c) Ghobrial, M. ; Harhammer, K. ; Mihovilovic, M. D. ; Schnürch, M. Chem. Commun. 2010, 46, 8836; (d) Correia, C. A. ; Li, C. J. Heterocycles 2010, 82, 555; (e) Richter, H. ; Rohlmann, R. ; García Mancheño, O. Chem. Eur. J. 2011, 17, 11622; (f) Xiang, S. -K. ; Zhang, B. ; Zhang, L. -H. ; Cui, Y. ; Jiao, N. Sci. China Chem. 2012, 55, 50; (g) Park, S. J. ; Price, J. R. ; Todd, M. H. J. Org. Chem. 2012, 77, 949; (h) Liu, X. ; Sun, B. ; Xie, Z. ; Qin, X. ; Liu, L. ; Lou, H. J. Org. Chem. 2013, 78, 3104; (i) Chen, W. ; Xie, Z. ; Zheng, H. ; Lou, H. ; Liu, L. Org. Lett. 2014, 16, 5988.
7. [7]
  Asymmetric cross-dehydrogenative coupling of cyclic benzylic ethers, see: Meng, Z. ; Sun, S. ; Yuan, H. ; Lou, H. ; Liu, L. Angew. Chem., Int. Ed. 2014, 53, 543.
8. [8]
  For cross-dehydrogenative coupling of unactivated cyclic ethers, see: (a) Wu, Z. ; Pi, C. ; Cui, X. ; Bai, J. ; Wu, Y. Adv. Synth. Catal. 2013, 355, 1971; (b) Huang, X. -F. ; Zhu, Z. -Q. ; Huang, Z. -Z. Tetrahedron 2013, 69, 8579; (c) Liu, D. ; Liu, C. ; Li, H. ; Lei, A. Chem. Commun. 2014, 50, 3623; (d) Wei, W. -T. ; Song, R. -J. ; Li, J. -H. Adv. Synth. Catal. 2014, 356, 1703; (e) Jin, J. ; MacMillan, D. W. C. Angew. Chem., Int. Ed. 2015, 54, 1565; (f) Jin, L. ; Feng, J. ; Lu, G. ; Cai, C. Adv. Synth. Catal. 2015, 357, 2105; (g) Niu, B. ; Zhao, W. ; Ding, Y. ; Bian, Z. ; Pittman Jr. C. U. ; Zhou, A. ; Ge, H. J. Org. Chem. 2015, 80, 7251; (h) Li, Q. ; Hu, W. ; Hu, R. ; Lu, H. ; Li, G. Org. Lett. 2017, 19, 4676; (i) Liu, S. ; Liu, A. ; Zhang, Y. ; Wang, W. Chem. Sci. 2017, 8, 4044; (j) Liu, D. ; Liu, C. ; Lei A. Angew. Chem., Int. Ed. 2013, 52, 4453; (k) Yang, Q. ; Choy, P. Y. ; Wu, Y. ; Fan, B. ; Kwong, F. Y. Org. Biomol. Chem. 2016, 14, 2608; (l) Zhang, L. ; Yi, H. ; Wang, J. ; Lei, A. J. Org. Chem. 2017, 82, 10704; (m) Wu, J. ; Zhou, Y. ; Zhou, Y. ; Chiang, C. -W. ; Lei, A. ACS Catal. 2017, 7, 8320; (n) Xie, Z. ; Cai, Y. ; Hu, H. ; Lin, C. ; Jiang, J. ; Chen, Z. ; Wang, L. ; Pan, Y. Org. Lett. 2013, 15, 4600; (o) Zhou, L. ; Tang, S. ; Qi, X. ; Lin, C. ; Liu, K. ; Liu, C. ; Lan, Y. ; Lei, A. Org. Lett. 2014, 16, 3404; (p) Tang, S. ; Wang, P. ; Li, H. ; Lei, A. Nat. Commun. 2016, 7, 11676.
9. [9]
  For cross-dehydrogenative coupling of acyclic benzylic ethers, see: (a) Liu, L. ; Floreancig, P. E. Org. Lett. 2009, 11, 3152; (b) Xie, Y. ; Yu, M. ; Zhang, Y. Synthesis 2011, 17, 2803.
10. [10]
  Diederich, F. ; Stang, P. J. ; Tykwinski, R. R. Acetylene Chemistry: Chemistry, Biology and Material Science, Wiley-VCH, Weinheim, 2005.
11. [11]
  Wan, M.; Meng, Z.; Lou, H.; Liu, L. Angew. Chem., Int. Ed. 2014, 53, 13845. doi: 10.1002/anie.201407083
12. [12]
  Zhang, Q.; Lv, J.; Luo, S. Acta Chim. Sinica 2016, 74, 61(in Chinese). doi: 10.3866/PKU.WHXB201511101
13. [13]
  Usugi, S.-i.; Yorimitsu, H.; Shinokubo, H.; Oshima, K. Bull. Chem. Soc. Jpn. 2002, 75, 2687. doi: 10.1246/bcsj.75.2687
14. [14]
  In-situ generated carbocation oxidation system shows better reactivity than pre-prepared one. At present, the origin of this difference in activity is still unknown.
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