仲酰胺经酰胺活化直接合成酮的普适性方法
发表时间:2020-11-22 作者:杭州新闻网

仲酰胺经酰胺活化直接合成酮的普适性方法

本文报道仲酰胺经去胺基烷基化反应直接合成酮的通用性方法. 这一新的C-C 键形成方法是基于Tf2O 对仲酰胺的活化及有机铈试剂对活化所形成活性中间体的加成而实现的. 该方法可用于各种酮的合成, 包括烷基-烷基酮、烷基-芳基酮、芳基-芳基酮、α,β-不饱和酮以及β-氯-α,β-不饱和酮等, 收率65%~90%. 研究表明, 除了有机铈试剂外, 碱性较弱的炔基硼试剂、温和亲核性的烯丙基三甲基硅烷以及低亲核性的苯乙烯均可与仲酰胺的活化中间体进行加成反应, 水解后生成相应的酮. 因此, 该方法具有较好的普适性和重要的合成应用价值. 基于实验结果和验证实验, 提出经由腈鎓中间体的可能反应机理. 本法使仲酰胺成为形式上的酰化试剂, 不但可与有机金属试剂反应, 还可与烯丙基三甲基硅烷和苯乙烯进行还原酰化反应.

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肖开炯, 黄应红, 黄培强. 仲酰胺经酰胺活化直接合成酮的普适性方法[J]. 化学学报, 2012, 70(18): 1917-1922.

Xiao Kaijiong, Huang Yinghong, Huang Peiqiang. General Direct Transformation of Secondary Amides to Ketones via Amide Activation[J]. Acta Chimica Sinica, 2012, 70(18): 1917-1922.

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参考文献

[1] Li, C.-J.; Trost, B. M. Proc. Natl. Acad. Sci. 2008, 105, 13197.

[2] For a recent review, see: Albrecht, L.; Jiang, H.; Jørgensen, K. A. Angew. Chem. Int. Ed. 2011, 50, 8492.

[3] For leading reviews, see: (a) Pellissier,H. Tetrahedron 2006, 62, 1619 and 2143;   " target=_blank>

仲酰胺经酰胺活化直接合成酮的普适性方法



(b) Guo, H.-C.; Ma, J.-A. Angew. Chem. Int. Ed. 2006, 45, 354.

[4] For a leading book, see: Multicomponent Reactions, Eds.; Zhu, J.-P.; Bienaymé, H., Wiley-VCH, Weinheim, 2005.   " target=_blank>

仲酰胺经酰胺活化直接合成酮的普适性方法



[5] Wender, P. A.; Croatt, M. P.; Witulski, B. Tetrahedron 2006, 62, 7505.   " target=_blank>

仲酰胺经酰胺活化直接合成酮的普适性方法



[6] Xu, C.-P.; Xiao, Z.-H.; Zhuo, B.-Q.; Wang, Y.-H.; Huang, P.-Q. Chem. Commun. 2010, 46, 7834.

[7] Liu, X.-K.; Zheng, X.; Ruan, Y.-P.; Ma, J.; Huang, P.-Q. Org. Biomol. Chem. 2012, 10, 1275.

[8] Wang, Y.-H.; Ye, J.-L.; Wang, A.-E; Huang, P.-Q. Org. Biomol. Chem. 2012, 10, 6504.

[9] Zheng. J.-L.; Liu, H.; Zhang, Y.-F.; Zhao, W.; Tong, J.-S.; Ruan, Y.-P.; Huang, P.-Q. Tetrahedron: Asymmetry 2011, 22, 257.   " target=_blank>

仲酰胺经酰胺活化直接合成酮的普适性方法



[10] Xiao, K.-J.; Luo, J.-M.; Ye, K.-Y.; Wang, Y.; Huang, P.-Q. Angew. Chem. Int. Ed. 2010, 49, 3037.

[11] (a) Xiao, K.-J.; Wang, Y.; Ye, K.-Y.; Huang, P.-Q. Chem. Eur. J. 2010, 16, 12792;   " target=_blank>

仲酰胺经酰胺活化直接合成酮的普适性方法



(b) Liao, J.-C.; Xiao, K.-J.; Zheng, X.; Huang, P.-Q. Tetrahedron 2012, 68, 5297.   " target=_blank>

仲酰胺经酰胺活化直接合成酮的普适性方法



[12] Xiao, K.-J.; Wang, A.-E; Huang, P.-Q. Angew. Chem. Int. Ed. 2012, 51, 8314.

[13] (a) Shi, Z.; Li, B.; Wan, X.; Cheng, J.; Fang, Z.; Cao, B.; Qin, C.; Wang, Y. Angew. Chem. Int. Ed. 2007, 46, 5554;

(b) Wang, X.; Leow, D.; Yu, J.-Q. J. Am. Chem. Soc. 2011, 133, 13864;

(c) Zultanski, S. L.; Fu, G. C. J. Am. Chem. Soc. 2011, 133, 15362;

(d) Chen, Q.; Ilies, L.; Nakamura, E. J. Am. Chem. Soc. 2011, 133, 428.

[14] For a recent review, see: Trost, B. M.; Brindle, C. S. Chem. Soc. Rev. 2010, 39, 1600.

[15] For selected reviews, see: (a) Abell, A. D.; Edmonds, M. K. In Organophosphorus Reagents; Ed.: Murphy, P. J., Oxford University Press, Oxford, 2004, p. 99;   " target=_blank>

仲酰胺经酰胺活化直接合成酮的普适性方法



(b) Kolodiazhnyi, O. I. Phosphorus Ylides: Chemistry and Applications in Organic Chemistry, Wiley-VCH, New York, 1999;   " target=_blank>

仲酰胺经酰胺活化直接合成酮的普适性方法



(c) Maryanoff, B. E.; Reitz, A. B. Chem. Rev. 1989, 89, 863.   " target=_blank>

仲酰胺经酰胺活化直接合成酮的普适性方法



[16] For a recent review, see: Krause, N.; Hoffmann-Röder, A. Synthesis 2001, 2, 171.

[17] (a) Nahm, S.; Weinreb, S. M. Tetrahedron Lett. 1981, 22, 3815. For a recent review, see:   

仲酰胺经酰胺活化直接合成酮的普适性方法



(b) Balasubramaniam, S.; Aiden, I. S. Synthesis 2008, 3707.

[18] Martín, R.; Romea, P.; Tey, C.; Urpí, F.; Vilarrasa, J. Synlett 1997, 1414.

[19] Bechara, W. S.; Pelletier, G.; Charette, A. B. Nat. Chem. 2012, 4, 228. This work appeared while we were submitting our own manuscript. The two methods are complementary as a general methodology for the transformation of secondary amides to ketones in terms of the scope, reaction conditions and nucleophiles used.

[20] Xiao, K.-J.; Wang, A.-E; Huang, Y.-H.; Huang, P.-Q. Asian J. Org. Chem. 2012, DOI: 10. 1002/ajoc. 201200066.

[21] For reviews on the chemistry of triflic acid and its derivatives, see: (a) Stang, P. J.; White, M. R. Aldrichimica Acta 1983, 16, 15.

(b) Baraznenok, I. L.; Nenajdenko, V. G.; Balenkova, E. S. Tetrahedron 2000, 56, 3077. For selected recent examples, see:   

仲酰胺经酰胺活化直接合成酮的普适性方法



(c) Charette, A. B.; Grenon, M.; Lemire, A.; Pourashraf, M.; Martel, J. J. Am. Chem. Soc. 2001, 123, 11829;

(d) Movassaghi, M.; Hill, M. D.; Ahmad, O. K. J. Am. Chem. Soc. 2007, 129, 10096;

(e) Zhou, H.-B.; Liu, G.-S.; Yao, Z.-J. J. Org. Chem. 2007, 72, 6270;

(f) Cui, S.-L.; Wang, J.; Wang, Y.-G. J. Am. Chem. Soc. 2008, 130, 13526;

(g) Barbe, G.; Charette, A. B. J. Am. Chem. Soc. 2008, 130, 18;

(h) Dong, Q.-L.; Liu, G.-S.; Zhou, H.-B.; Lin, C.; Yao, Z.-J. Tetrahedron Lett. 2008, 10, 1636.

[22] Harder, I.; Hanack, M. Chem. Ber. 1984, 117, 3004.

[23] Medley, J. W.; Movassaghi, M. J. Org. Chem. 2009, 74, 1341.

[24] For the preparation of organocerium reagents from RLi, see: (a) Imamoto, T.; Sugiura, Y.; Takiyama, N. Tetrahedron Lett. 1984, 25, 4233. For the preparation of organocerium complexs from RMgX, see:   

仲酰胺经酰胺活化直接合成酮的普适性方法



(b) Imamoto, T.; Takiyama, N.; Nakamura, K.; Hatajima, T.; Kamiya, Y. J. Am. Chem. Soc. 1989, 111, 4392. For a recent review, see:   " target=_blank>

仲酰胺经酰胺活化直接合成酮的普适性方法



(c) Bartoli, G.; Marcantoni, E.; Marcolini, M.; Sambri, L. Chem. Rev. 2010, 110, 6104.

[25] Enones, Eds.: Patai, S.; Rappoport, Z., Wiley, Chichester, 1989, Vol. 1.   " target=_blank>

仲酰胺经酰胺活化直接合成酮的普适性方法



[26] (a) Pohland, A. E.; Benson, W. R. Tetrahedron 1966, 66, 161;

(b) Iwai, T.; Fujihara, T.; Terao, J.; Tsuji, Y. J. Am. Chem. Soc. 2012, 134, 1268.

[27] Yamaguchi, M.; Waseda, T.; Hirao, I. Chem. Lett. 1983, 12, 35.   

仲酰胺经酰胺活化直接合成酮的普适性方法



[28] For the synthesis of furans, see: (a) Jeevanandam, A.; Narkunan, K.; Ling, Y.-C. J. Org. Chem. 2001, 66, 6014;

(b) Kel’in, A. V.; Gevorgyan, V. J. Org. Chem. 2002, 67, 95. For the synthesis of pyrazoles, see:

(c) Wang, X.; Tan, J.; Zhang, L. Org. Lett. 2000, 2, 3107;

(d) Grotjahn, D. B.; Van, S.; Combs, D.; Lev, D. A.; Schneider, C.; Rideout, M.; Meyer, C.; Hernandez, G.; Mejorado, L. J. Org. Chem. 2002, 67, 9200.

[29] For a related mechanism involving an intramolecular hydride transfer to give an immonium ion, see: Heathcock, C. H.; Kath, J. C.; Ruggeri, R. B. J. Org. Chem. 1995, 60, 1120.

[30] Fukuda, Y.; Utimoto, K. Bull. Chem. Soc. Jpn. 1991, 64, 2013.

[31] Hosseini-Sarvari, M.; Mardaneh, Z. Bull. Chem. Soc. Jpn. 2011, 84, 778.

[32] Liu, J.; Peng, X.; Sun, W.; Zhao, Y.; Xia, C. Org. Lett. 2008, 18, 3933.

[33] Kawakami, T.; Miyatake, M.; Shibata, I.; Baba, A.; Matsuda, H. J. Org. Chem. 1996, 61, 376.

 

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