Citation: Peng Lifen, Zhang Siwei, Wang Binghao, Xun Mengshuo, Tang Zilong, Jiao Yinchun, Xu Xinhua. Synthesis of Cyclic Phenyl Polyynes: Ph₂P-Deprotection/Intramolecular Eglington Coupling Cyclization[J]. Chinese Journal of Organic Chemistry, ;2018, 38(2): 519-525. doi: 10.6023/cjoc201708011 shu

Synthesis of Cyclic Phenyl Polyynes: Ph₂P-Deprotection/Intramolecular Eglington Coupling Cyclization

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: 7 August 2017
Revised Date: 28 September 2017
Available Online: 20 February 2017
Fund Project: the National Natural Science Foundation of China 21402048Project supported by the General Project of Hunan Education Department (No. 17C0629), the Doctoral Foundation of Hunan University of Science and Technology (No. E51693), the Open Foundation of Key Laboratory of Theoretical Organic Chemistry and Functional Molecule of Ministry of Education, Hunan University of Science and Technology (No. E21630) and the National Natural Science Foundation of China (No. 21402048)the Open Foundation of Key Laboratory of Theoretical Organic Chemistry and Functional Molecule of Ministry of Education, Hunan University of Science and Technology E21630the General Project of Hunan Education Department 17C0629the Doctoral Foundation of Hunan University of Science and Technology E51693

Figures(4)

Ph₂P (O)-deprotection/intramolecular Eglington coupling cyclization, proceeding in one-pot manner, can be applied to synthesize cyclic phenyl polyynes. Compared to Micheal M. Haley's stepwise desilylation/Eglington coupling reaction, the polar Ph₂P (O) protecting group enabled facile seperation of product from remaining starting compound for their different polarity, and it also led to easy separation of target compound because the amont of by-products which showed similar R_f to target compound decreased. Furthermore, our one-pot reaction, avoiding the workup after Ph₂P (O)-deprotection and reducing losses of materials, increased the yield of cyclic aromatic polyynes. This method showed some other outstanding features including easy synthesis of intermediates and mild reaction conditions.
- one-pot reaction,
- diphenylphosphoryl protecting group,
- cyclic phenyl polyyne
1. [1]
  Diederich, F. ; Stang, P. J. ; Tykwinski, R. R. Acetylene Chemistry, Willey-VCH Verlag GmbH & CO. KgaA, Weinheim, 2005.
2. [2]
  Fischer, M.; Lieser, G.; Rapp, A.; Schnell, I.; Mamdouh, W.; Feyter, S. D.; Schryver, F. C.; H ger, S. J. Am. Chem. Soc. 2004, 126, 214. doi: 10.1021/ja038484x
3. [3]
  Wan, W. B.; Brand, S. C.; Pak, J. J.; Haley, M. M. Chem. -Eur. J. 2005, 6, 2044.
4. [4]
  Zhou, Q.; Carroll, P. J.; Swager, T. M. J. Org. Chem. 1994, 59, 1294. doi: 10.1021/jo00085a016
5. [5]
  (a) Glaser, C. Chem. Ber. 1869, 2, 422.
  (b) Hay, A. S. J. Org. Chem. 1962, 27, 3320.
  (c) Eglinton, G. ; McRae, W. Adv. Org. Chem. 1963, 4, 225.
  (d) Vö gtle, F. ; Berscheid, R. Synthesis 1992, 58.
6. [6]
  Haley, M. M.; Bell, M. L.; English, J. J.; Johnson, C. A.; Weakley, T. J. R. J. Am. Chem. Soc. 1997, 119, 2956. doi: 10.1021/ja964048h
7. [7]
  Orita, A.; Taniguchi, H.; Otera, J. Chem. -Asian J. 2006, 1, 430. doi: 10.1002/(ISSN)1861-471X
8. [8]
  Peng, L. -F.; Xu, F.; Suzuma, Y.; Orita, A.; Otera, J. J. Org. Chem. 2013, 78, 12802. doi: 10.1021/jo402176w
9. [9]
  (a) Eglinton, G. ; Galbraith, A. R. Chem. Ind. 1956, 737.
  (b) Behr, O. M. ; Eglinton, G. ; Galbraith, A. R. ; Raphael. R. A. J. Chem. Soc. 1960, 3614.
  (c) Altmann, M. ; Friedrich, J. ; Beer, F. ; Reuter, R. ; Enkelmann, V. ; Bunz, U. H. F. J. Am. Chem. Soc. 1997, 119, 1472.
10. [10]
  Orita, A.; Miyamoto, K.; Nakashima, M.; Ye, F. -G.; Otera, J. Adv. Synth. Catal. 2004, 346, 767. doi: 10.1002/(ISSN)1615-4169
11. [11]
  Peng, L. -F.; Xu, F.; Shinohara, K.; Orita, A.; Otera, J. Chem. Lett. 2014, 43, 1610. doi: 10.1246/cl.140579
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沈阳化工大学材料科学与工程学院沈阳 110142

Synthesis of Cyclic Phenyl Polyynes: Ph2P-Deprotection/Intramolecular Eglington Coupling Cyclization

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Synthesis of Cyclic Phenyl Polyynes: Ph₂P-Deprotection/Intramolecular Eglington Coupling Cyclization