Chinese Journal of Organic Chemistry >
Nickel-Catalyzed Reductive Methylation of Alkyl Acid with Methyl p-Tosylate
Received date: 2017-03-24
Revised date: 2017-04-16
Online published: 2017-05-17
Supported by
Project supported by the National Natural Science Foundation of China (No.61204020) and the Innovation Program of Shanghai Municipal Education Commission (No.15ZZ047).
Methyl group is the smallest carbon substituent that plays important roles in many compounds. Conversion of a carboxylic acid into a ketone is a fundamental transformation in organic chemistry. This functional group change is usually performed indirectly by activating the carboxylic acid into an acyl chloride or into a Weinreb amide, and then by nucleophilic attack with an organometallic reagent. However, direct conversion of a carboxylic acid into a ketone can be achieved in one-step reaction using at least 2 equiv. of an organolithium reagent at low temperature and producing much tertiary alcohol. Herein, methylation of alkyl acid under Ni-catalyzed reductive coupling conditions using methyl p-methyl tosylate as the methylation reagent was reported to yield methylated ketones. Moderate yields as well as good functional group tolerance were observed under the present mild and easy-to-operate reaction conditions.
Key words： methylation; nickel-catalyzed; alkyl acid; reductive coupling
Gu Jun , Liu Jiandong , Sun Yuren , Wang Hongyu . Nickel-Catalyzed Reductive Methylation of Alkyl Acid with Methyl p-Tosylate[J]. Chinese Journal of Organic Chemistry, 2017 , 37(7) : 1830 -1834 . DOI: 10.6023/cjoc201703042
[1] Sheng, W.; Jin, C.; Shan, S.; Jia, Y.; Gao, J. Chin. J. Org. Chem. 2016, 36, 325(in Chinese). (盛卫坚, 金城安, 单尚, 贾义霞, 高建荣, 有机化学, 2016, 36, 325.)
[2] Ni, C.; Zhu, L.; Hu, J. Acta Chim. Sinica 2015, 73, 90(in Chinese). (倪传法, 朱林桂, 胡金波, 化学学报, 2015, 73, 90.)
[3] Gou, B.; Yang, C.; Zhang, L.; Xia, W. Acta Chim. Sinica 2017, 75, 66(in Chinese). (苟宝权, 杨超, 张磊, 夏吾炯, 化学学报, 2017, 75, 66.)
[4] Rong, J.; Ni, C.; Wang, Y.; Kuang, C.; Gu, Y.; Hu, J. Acta Chim. Sinica 2017, 75, 105(in Chinese). (荣健, 倪传法, 王云泽,匡翠文, 顾玉诚, 胡金波, 化学学报, 2017, 75, 105.)
[5] Zhuang, H.; Zeng, R.; Zou, J. Chin. J. Org. Chem. 2016, 34, 368.
[6] Heike, S.; Tim, C. Angew. Chem., Int. Ed. 2013, 52, 2.
[7] Barreiro, E. J.; Kümmerle, A. E.; Fraga, C. A. M. Chem. Rev. 2011, 111, 5215.
[8] Peretti, K. L.; Ajiro, H.; Cohen, C. T.; Lobkovsky, E. B.; Coates, G. W. J. Am. Chem. Soc. 2005, 127, 11566.
[9] Nicholson, J. W.; Wilson, A. D. J. Chem. Educ. 2004, 81, 1362.
[10] Wilkinson, M. C. Org. Lett. 2011, 13, 2232.
[11] Park, A.; Park, K.; Kim, Y.; Lee, S. Org. Lett. 2011, 13, 944.
[12] Gooβen, L.; Rodriguez, N.; Gooβen, K. Angew. Chem., Int. Ed. 2008, 47, 3100.
[13] Posner, G. H.; Whitten, C. E.; McFarland, P. E. J. Am. Chem. Soc. 1972, 94, 5106.
[14] Wang, X.; Zhang, L.; Sun, X.; Xu, Y.; Krishnamurthy, D.; Senanayake, C. H. Org. Lett. 2005, 7, 5593.
[15] Ryu, I.; Ikebe, M.; Sonoda, N.; Yamato, S.; Yamamura, G.; Komatsu, M. Tetrahedron Lett. 2002, 43, 1257.
[16] Dieter, R. K. Tetrahedron 1999, 55, 4177.
[17] Nahm, S.; Weinreb, S. M. Tetrahedron Lett. 1981, 22, 3815.
[18] Kangani, C. O.; Kelley, D. E.; Day, B. W. Tetrahedron Lett. 2006, 6289.
[19] Qu, B.; Collum, D. B. J. Org. Chem. 2006, 71, 7117.
[20] Alonso, F.; Lorenzo, E.; Yus, M. J. Org. Chem. 1996, 61, 6058.
[21] Gilman, H.; van Ess, P. R. J. Am. Chem. Soc. 1933, 55, 1258.
[22] Tegner, C. Acta Chem. Scand 1952, 6, 782.
[23] Jorgenson, M. J. Org. React. 1970, 18, 1.
[24] Bare, T. M.; House, H. O. Org. Synth. 1973, 5, 775.
[25] Lubell, W. D.; Rapoport, H. J. Am. Chem. Soc. 1988, 110, 7447
[26] (a) Gu, J.; Wang, X.; Xue, W.; Gong, H. Org. Chem. Front. 2015, 2, 1411.
(b) Everson, D. A.; Weix, D. J. J. Org. Chem. 2014, 79, 4793.
(c) Knappke, C. E.; Grupe, S.; Gärtner, D.; Corpet, M.; Gosmini, C.; Jacobi von Wangelin, A. Chem. Eur. J. 2014, 20, 6828.
(d) Weix, D. J. Acc. Chem. Res. 2015, 48, 1767.
(e) Moragas, T.; Correa, A.; Martin, R. Chem. Eur. J. 2014, 20, 8242.
(f) Wang, X.; Dai, Y.; Gong, H. Top. Curr. Chem. 2016, 374, 43.
[27] Fillon, F.; Gosmini, C.; Perichon, J. Tetrahedron 2003, 59, 8199.
[28] Hsieh, J.-H.; Cheng, C.-H. Chem. Commun. 2005, 4554.
[29] Wotal, A.; Weix, D. J. Org. Lett. 2012, 14, 1476.
[30] Wu, F.; Gong, H. Org. Lett. 2012, 14, 3044.
[31] Yin, H.; Zhao, C.; You, H.; Lin, Q.; Gong, H. Chem. Commun. 2012, 48, 7034.
[32] Zhao, C.; Jia, X.; Wang, X.; Gong, H. J. Am. Chem. Soc. 2013, 136, 17645.
[33] Lu, W.; Liang, Z.; Zhang, Y.; Wu, F.; Qian, Q.; Gong, H. Synthesis 2013, 45, 2234.
[34] Liang, Z.; Xue, W.; Lin, K.; Gong, H. Org. Lett. 2014, 16, 5620.
[35] Jia, X.; Zhang, X.; Qian, Q.; Gong, H. Chem. Commun. 2015, 51, 10302.
[36] Christelle, P.; François, C.; Bertrand, C. Org. Lett. 2001, 3, 803.
/
| 〈 |
|
〉 |
