金催化氧化末端炔烃合成α-乙酰氧基甲基酮方法研究
收稿日期: 2013-08-11
修回日期: 2013-11-04
网络出版日期: 2013-11-14
基金资助
湖南省自然科学基金（No. 11JJ2009）和湖南省高校科技创新团队资助项目.
Gold(I)-Catalyzed Intermolecular Oxidation of Terminal Alkynes：Synthesis of α-Acetoxy Ketones
Received date: 2013-08-11
Revised date: 2013-11-04
Online published: 2013-11-14
Supported by
Project supported by the Natural Science Foundation of Hunan Province (No. 11JJ2009) and the Sci-Tech Innovation Teams in Universities of Hunan Province.
采用Ph3PAuNTf2作为催化剂，8-甲基喹啉氮氧化物为氧化剂，甲基磺酸为添加酸，金催化氧化末端炔烃与乙酸分子反应，室温下高效合成了一系列α-乙酰氧基甲基酮化合物. 考察了氧化剂、催化剂结构、催化剂用量等因素对反应的影响，确定了最优反应条件，最高收率为90%. 提出了α-羰基金卡宾对乙酸分子O—H键的卡宾反应机理. 该方法具有操作简单、条件温和、产率高等特点，为含有α-乙酰氧基甲基酮结构的化合物合成提供了一条新的途径.
关键词： 金催化; 炔烃; 分子间氧化; α-羰基金卡宾中间体; α-乙酰氧基甲基酮
王小勇 , 李治章 . 金催化氧化末端炔烃合成α-乙酰氧基甲基酮方法研究[J]. 有机化学, 2014 , 34(3) : 566 -571 . DOI: 10.6023/cjoc201308013
In the presence of Ph3PAuNTf2, 8-methylquinoline-N-oxide and MsOH, various of terminal alkynes were efficiently converted into the corresponding α-acetoxy ketones. The influences of oxidant, catalyst structure, catalyst loading and reaction media on the reaction were investigated, and the optimal reaction conditions were also obtained. The reaction is proposed to proceed via α-oxo gold carbene intermolecular reaction with acetic acids. The reaction method with its advantages of simple procedure, mild reaction conditions and high yield provides a novel valuable approach to α-acetoxy ketones from terminal alkynes.
[1] Fürstner, A.; Davies, P. W. Angew. Chem., Int. Ed. 2007, 46, 3410.
[2] Hashmi, A. S. K. Chem. Rev. 2007, 107, 3180.
[3] Gorin, D. J.; Sherry, B. D.; Toste, F. D. Chem. Rev. 2008, 108, 3351.
[4] Li, Z.; Brouwer, C.; He, C. Chem. Rev. 2008, 108, 3239.
[5] Huang, H.; Zhou, Y.; Liu, H. Beilstein J. Org. Chem. 2011, 7, 897.
[6] Lu, B.-L.; Dai, L.; Shi, M. Chem. Soc. Rev. 2012, 41, 3318.
[7] Ye, L.; He, W.; Zhang, L. J. Am. Chem. Soc. 2010, 132, 8550.
[8] Ye, L.; He, W.; Zhang, L. Angew. Chem., Int. Ed. 2011, 50, 3236.
[9] Qian, D.; Zhang, J. Chem. Commun. 2011, 47, 11152.
[10] He, W.; Li, C.; Zhang, L. J. Am. Chem. Soc. 2011, 133, 8482.
[11] Qian, D.; Zhang, J. Chem. Commun. 2012, 48, 7082.
[12] He, W.; Xie, L.; Xu, Y.; Xiang, J.; Zhang, L. Org. Biomol. Chem. 2012, 10, 3168.
[13] Xu, M.; Ren, T.-T.; Li, C.-Y. Org. Lett. 2012, 14, 4902.
[14] Fu, J.; Shang, H.; Wang, Z.; Chang, L.; Shao, W.; Yang, Z.; Tang, Y. Angew. Chem., Int. Ed. 2013, 52, 4198.
[15] Xie, L.; Liang, Z.; Yan, D.; He, W.; Xiang, J. Synlett 2013, 1809.
[16] Li, G.; Zhang, L. Angew. Chem., Int. Ed. 2007, 46, 5156.
[17] Shapiro, N. D.; Toste, F. D. J. Am. Chem. Soc. 2007, 129, 4160.
[18] Li, C.-W.; Pati, K.; Lin, G.-Y.; Sohel, S. M. A.; Hung, H.-H.; Liu, R.-S. Angew. Chem., Int. Ed. 2010, 49, 9891.
[19] Yeom, H.-S.; Lee, J.-E.; Shin, S. Angew. Chem., Int. Ed. 2008, 47, 7040.
[20] Mukherjee, A.; Dateer, R. B.; Chaudhuri, R.; Bhunia, S.; Karad, S. N.; Liu, R.-S. J. Am. Chem. Soc. 2011, 133, 15372.
[21] Xiao, J.; Li, X. Angew. Chem., Int. Ed. 2011, 50, 7226.
[22] Green, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, Wiley, New York, 1991.
[23] Holshouser, M. H.; Kolb, M. J. Pharm. Sci. 1986, 75, 619.
[24] Rather, J. B.; Reid, E. E. J. Am. Chem. Soc. 1919, 41, 75.
[25] Paulissen, R.; Reimlinger, H.; Hayez, E.; Hubert, A. J.; Teyssié, P. Tetrahedron Lett. 1973, 14, 2233.
[26] Shinada, T.; Kawakami, T.; Sakai, H.; Takada, I.; Ohfune, Y. Tetrahedron Lett. 1998, 39, 3757.
[27] Rubottom, G. M.; Grube, J. M.; Kincaid, K. Synth. Commun. 1976, 6, 59.
[28] Demir, A. S.; Camkerten, N.; Akgun, H.; Tanyeli, C.; Mahasneh, A. S.; Watt, D. S. Synth. Commun. 1990, 20, 2279.
[29] Lee, J. C.; Jin, Y. S.; Choi, J.-H. Chem. Commun. 2001, 956.
[30] Mo, D.-L.; Dai, L.-X.; Hou, X.-L. Tetrahedron Lett. 2009, 50, 5578.
[31] Sheng, J.; Li, X.; Tang, M.; Gao, B.; Huang, G. Synthesis 2007, 1165.
[32] Ochiai, M.; Takeuchi, Y.; Katayama, T.; Sueda, T.; Miyamoto, K. K. J. Am. Chem. Soc. 2005, 127, 12244.
[33] Deng, G.; Luo, J. Tetrahedron 2013, 69, 5937.
[34] Kaila, N.; Janz, K.; De Bernardo, S.; Bedard, P. W.; Camphausen, R. T.; Tam, S.; Tsao, D. H. H.; Keith, J. C.; Nickerson-Nutter, C.; Shilling, A.; Young-Sciame, R.; Wang, Q. J. Med. Chem. 2006, 50, 21.
/
| 〈 |
|
〉 |
