Citation: Peng Lifen, Peng Chao, Wang Ming, Tang Zilong, Jiao Yinchun, Xu Xinhua. Phosphoryl Protecting Group Enabled Facile Synthesis of Unsymmetrical 1, 3-Diynes by Selective Hay Coupling[J]. Chinese Journal of Organic Chemistry, ;2018, 38(11): 3048-3055. doi: 10.6023/cjoc201805009 shu

Phosphoryl Protecting Group Enabled Facile Synthesis of Unsymmetrical 1, 3-Diynes by Selective Hay Coupling

Peng Lifen ^a,, ,
Peng Chao ^a ,
Wang Ming ^a ,
Tang Zilong ^a,, ,
Jiao Yinchun ^a ,
Xu Xinhua ^b

a.
Key Laboratory of Theoretical Organic Chemistry and Functional Molecule of Ministry of Education, Hunan Provincial Key Laboratory of Controllable Preparation and Functional Application of Fine Polymers, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201
b.
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082

Corresponding author: Peng Lifen, 1060137@hnust.edu.cn Tang Zilong, zltang@hnust.edu.cn
Received Date: 2 May 2018
Revised Date: 30 May 2018
Available Online: 5 November 2018
Fund Project: Project supported by the National Natural Science Foundation of China (No. 21402048), the Natural Science Fund Youth Project of Hunan Province (No. 2018JJ3145), the General Project of Hunan Education Department (No. 17C0629) and the Doctoral Foundation of Hunan University of Science and Technology (No. E51693)the General Project of Hunan Education Department 17C0629the Natural Science Fund Youth Project of Hunan Province 2018JJ3145the National Natural Science Foundation of China 21402048the Doctoral Foundation of Hunan University of Science and Technology E51693

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A selective Hay coupling reaction of aromatic terminal acetylenes and monophosphoryl-protected diynes was developed. The polarity of Ph₂P(O) realized facile isolation of the desired unsymmetrical 1, 3-diynes from by-products. The low reactivity of monophosphoryl-protected diynes reduced the oxidative homocoupling of itself and enhanced the yields of desired products. A number of aromatic terminal acetylenes and monophosphoryl-protected diynes were tolerated in this reaction, and all the corresponding unsymmetrical 1, 3-diynes could be obtained in moderate to good yields. The unsymmetrical 1, 3-diynes could be applied to synthesize unsymmetrical yne-diynes and cyclic polyynes.
- Hay coupling,
- unsymmetrical 1, 3-diyne,
- terminal acetylene,
- phosphoryl protecting group
1. [1]
  Stang, P. J.; Diederich, F. Modern Acetylene Chemistry, VCH, Weinheim, 1995.
2. [2]
  Shi, W.; Lei, A.-W. Tetrahedron Lett. 2014, 55, 2763. doi: 10.1016/j.tetlet.2014.03.022
3. [3]
  (a) Ito, A.; Cui, B.; Chavez, D.; Chai, H. B.; Shin, Y. G.; Kawanishi, K.; Kardono, L. B.; Riswan, S.; Farnsworth, N. R.; Cordell, G. A.; Pezzuto, J. M.; Kinghorn, A. D. J. Nat. Prod. 2001, 64, 246.
  (b) Evano, G.; Blanchard, N. Copper-Mediated Cross-Coupling Reactions, John Wiley & Sons, Inc., Hoboken, NJ, 2014.
  (c) Siemsen, P.; Livingston, R. C.; Diederich, F. Angew. Chem. Int. Ed. 2000, 39, 2632.
4. [4]
  Guo, L.; Song, L.; Wang, Z.; Zhao, W.; Mao, W.; Yin, M. Chem. Biol. Interact. 2009, 181, 138. doi: 10.1016/j.cbi.2009.04.015
5. [5]
  (a) Katano, M.; Yamamoto, H.; Matsunaga, H.; Mori, M.; Takata, K.; Nakamura, M. Gan to Kagaku Ryoho 1990, 17, 1045.
  (b) Matsunaga, H.; Saita, T.; Naguo, F.; Mori, M.; Katano, M. Cancer Chemother. Pharmacol. 1995, 35, 291.
6. [6]
  (a) Yadav, J. S.; Kumaraswamy, B.; Sathish Reddy, A.; Srihari, P.; Janakiram, R. V.; Kalivendi, S. V. J. Org. Chem. 2011, 76, 2568.
  (b) Srihari, P.; Sathish Reddy, A.; Deepthi, Y.; Kalivendi, S. Tetrahedron Lett. 2013, 54, 5616.
7. [7]
  Gangadhar, P.; Reddy, S. A.; Srihari, P. Tetrahedron 2016, 72, 5807. doi: 10.1016/j.tet.2016.08.009
8. [8]
  (a) Fang, J.-K.; Sun, T.-X.; Tian, Y.; Zhang, Y.-J.; Jin, C.-F.; Xu, Z.-M.; Hu, X.-Y.; Wang, H.-B. Mater. Chem. Phys. 2017, 195, 1.
  (b) Peng, L.-F.; Wang, B.-H.; Wang, M.; Tang, Z.-L.; Jiang, Y.-Z.; Jiao, Y.-C.; Xu, X.-H. J. Chem. Res. 2018, 42, 235.
  (c) Peng, L.-F.; Lei, J.-Y.; Wu, L.; Tang, Z.-L.; Luo, Z.-P.; Jiao, Y.-C.; Xu, X.-H. J. Chem. Res. 2018, 42, 271.
9. [9]
  Pati, A. K.; Mohapatra, M.; Ghosh, P.; Gharpure, S. J.; Mishra, A. K. J. Phys. Chem. A 2013, 117, 6548. doi: 10.1021/jp404809g
10. [10]
11. [11]
  (a) Li, Y.-N.; Wang, J.-L.; He, L.-N. Tetrahedron Lett. 2011, 52, 3485.
  (b) Yadav, J. S.; Reddy, B. V. S.; Reddy, K. B.; Gayathri, K. U.; Prasad, A. R. Tetrahedron Lett. 2003, 44, 6493.
12. [12]
  (a) Hay, A. J. Org. Chem. 1960, 25, 1275.
  (b) Abe, H.; Kurokawa, H.; Chida, Y.; Inouye, M. J. Org. Chem. 2011, 76, 309.
13. [13]
  (a) Hay, A. S. J. Org. Chem. 1962, 27, 3320.
  (b) Montierth, J. M.; DeMario, D. R.; Kurth, M. J.; Schore, N. E. Tetrahedron 1998, 54, 11741.
14. [14]
  (a) Bandyopadhyay, A.; Varghese, B.; Sankararaman, S. J. Org. Chem. 2006, 71, 4544.
  (b) Cahiez, G.; Moyeux, A. Chem. Rev. 2010, 110, 1435.
15. [15]
  (a) Allen, S. E.; Walvoord, R. R.; Padilla-Salinas, R.; Kozlowski, M. C. Chem. Rev. 2013, 113, 6234.
  (b) Siemsen, P.; Livingston, R. C.; Diederich, F. Angew. Chem., Int. Ed. 2000, 39, 2632.
  (c) Stefani, H. A.; Guarezemini, A. S.; Cella, R. Tetrahedron 2010, 66, 7871.
  (d) Jia, X.; Yin, K.; Li, C.; Li, J.; Bian, H. Green Chem. 2011, 13, 2175.
  (e) Kamata, K.; Yamaguchi, S.; Kotani, M.; Yamaguchi, K.; Mizuno, N. Angew. Chem., Int. Ed. 2008, 47, 2407.
  (f) Crowley, J. D.; Goldup, S. M.; Gowans, N. D.; Leigh, D. A.; Ronaldson, V. E.; Slawin, A. M. Z. J. Am. Chem. Soc. 2010, 132, 6243.
  (g) Gao, H.-Y.; Wagner, H.; Zhong, D.; Franke, J.-H.; Studer, A.; Fuchs, H. Angew. Chem., Int. Ed. 2013, 52, 4024.
  (h) Zhang, S.; Liu, X.; Wang, T. Adv. Synth. Catal. 2011, 353, 1463.
  (i) Balamurugan, R.; Naveen, N.; Manojveer, S.; Nama, M. V. Aust. J. Chem. 2011, 64, 567.
  (j) Wong, W.-Y.; Lu, G.-L.; Choi, K.-H.; Guo, Y.-H. J. Organomet. Chem. 2005, 690, 177.
  (k) Navale, B. S.; Bhat, R. G. RSC Adv. 2013, 3, 5220.
  (l) Liu, Y.; Wang, C.; Wang, X.; Wan, J.-P. Tetrahedron Lett. 2013, 54, 3953.
16. [16]
  (a) Yin, W.; He, C.; Chen, M.; Zhang, H.; Lei, A. Org. Lett. 2009, 11, 709.
  (b) Suarez, J. R.; Collado-Sanz, D.; Cardenas, D. J.; Chiara, J. L. J. Org. Chem. 2015, 80, 1098.
  (c) Balaraman, K.; Kesavan, V. Synthesis 2010, 3461.
  (d) Lampkowski, J. S.; Durham, C. E.; Padilla, M. S.; Young, D. D. Org. Biomol. Chem. 2015, 13, 424.
17. [17]
  (a) Cadiot, P.; Chodkiewicz, W. Chemistry of Acetylenes, Marcel Dekker, New York, 1969.
  (b) Sindhu, K. S.; Thankachan, A. P.; Sajitha, P. S.; Anilkumar, G. Org. Biomol. Chem. 2015, 13, 6891.
  (c) Yu, M.; Pan, D.; Jia, W.; Chen, W.; Jiao, N. Tetrahedron Lett. 2010, 51, 1287.
18. [18]
  (a) Peng, H.-H.; Xi, Y.-M.; Ronaghi, N.; Dong, B.-L.; Akhmedov, N. G.; Shi, X.-D. J. Am. Chem. Soc. 2014, 136, 13174.
  (b) Vilhanová, B.; Václavík, J.; Artiglia, L.; Ranocchiari, M.; Togni, A.; Bokhoven, J. A. ACS Catal. 2017, 7, 3414.
19. [19]
  Lampkowski, J. S.; Uthappa, D. M.; Halonski, J. F.; Maza, J. C.; Young, D. D. J. Org. Chem. 2016, 81, 12520. doi: 10.1021/acs.joc.6b02407
20. [20]
  Su, L.-B.; Dong, J.-Y.; Liu, L.; Sun, M.-L.; Qiu, R.-H.; Zhou, Y.-B.; Yin, S.-F. J. Am. Chem. Soc. 2016, 138, 12348. doi: 10.1021/jacs.6b07984
21. [21]
  Wan, J.-P.; Cao, S.; Jing, Y.-F. Appl. Organomet. Chem. 2014, 28, 631. doi: 10.1002/aoc.v28.8
22. [22]
  Yang, X.; Matsuo, D.; Suzuma, Y.; Fang, J.-K.; Xu, F.; Orita, A.; Otera, J. Synlett 2011, 2402.
23. [23]
  Peng, L.-F.; Xu, F.; Suzuma, Y.; Orita, A.; Otera, J. J. Org. Chem. 2013, 78, 12802. doi: 10.1021/jo402176w
24. [24]
  Peng, L.-F.; Xu, F.; Shinohara, K.; Orita, A.; Otera, J. Chem. Lett. 2014, 43, 1610. doi: 10.1246/cl.140579
25. [25]
  Peng, L.-F.; Xu, F.; Shinohara, K.; Orita, A.; Otera, J. Org. Chem. Front. 2015, 2, 248. doi: 10.1039/C4QO00325J
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