SIOC English
有机化学
高级检索

有机化学 >

2013 , Vol. 33 >Issue 06: 1291 - 1297

DOI: https://doi.org/10.6023/cjoc201304019

研究论文

3-羟基哌啶N,O-缩醛的不对称烯丙基化反应及在Epiquinamide和(+)-Febrifugine合成中的应用

  • 冯涛 ,
  • 司长梅 ,
  • 刘如成 ,
  • 范翔 ,
  • 魏邦国
展开
  • a 复旦大学化学系 上海 200043;
    b 华东理工大学生物工程学院 上海 200237

收稿日期: 2013-04-15

  修回日期: 2013-05-03

  网络出版日期: 2013-05-06

基金资助

国家自然科学基金(Nos.21272041, 21072034)资助项目.

收起

Asymmetric Allylation of N,O-Acetal and Application in the Synthesis of Epiquinamide and (+)-Febrifugine

  • Feng Tao ,
  • Si Changmei ,
  • Liu Rucheng ,
  • Fan Xiang ,
  • Wei Bangguo
Expand
  • a Department of Chemistry, Fudan University, Shanghai 200043;
    b School of Biotechnology, East China University of Science and Technology, Shanghai 200237

Received date: 2013-04-15

  Revised date: 2013-05-03

  Online published: 2013-05-06

Supported by

Project supported by the National Natural Science Foundation of China (Nos.21272041, 21072034).

Fold

摘要

探索了N,O-缩醛7 C-2位的不对称烯丙基化的条件, 建立了路易斯酸催化条件下高选择性烯丙基化方法(产率73%, dr 94∶6).并以此为关键反应, 合成了制备(-)-Epiquinamide (1)的关键中间体21.作为延续性工作, 建立了一条由(2S,3S)和(2S,3R)-9差向异构体混合物制备光学纯(+)-Febrifugine (3)的方法.从而开发了一条以廉价谷氨酸为原料制备克级常山碱的可能途径.

关键词： N,O-缩醛; 烯丙基化; 谷氨酸; Epiquinamide; (+)-Febrifugine

本文引用格式

冯涛 , 司长梅 , 刘如成 , 范翔 , 魏邦国 . 3-羟基哌啶N,O-缩醛的不对称烯丙基化反应及在Epiquinamide和(+)-Febrifugine合成中的应用[J]. 有机化学, 2013 , 33(06) : 1291 -1297 . DOI: 10.6023/cjoc201304019

Abstract

Lewis acid catalyzed asymmetric allylation of N,O-acetal 7 with allyltrimethylsilane was developed for the synthesis of compounds 9, 10 and 16 with high disasterselectivities.A key middle compound 21 for synthesis of (-)-epiquinamide (1) was easily prepared from allylation product 16.In continuation of our work, a convenient method for synthesis of (+)-febrifugine (3) was also described from the mixture of (2S,3S) and (2S,3R)-9.Therefore, a possible approach for gram scale preparation of (+)-febrifugine (3) from glutamic acid was achieved.

Key words： N,O-acetal; allylation; glutamic acid; Epiquinamide; (+)-Febrifugine

参考文献

[1] (a) Fitch, R.W.; Garraffo, H.M.; Spande, T.F. J.Nat.Prod.2003, 66, 1345.(b) Huang, P.-Q.; Guo, Z.-Q.; Ruan, Y.-P.Org.Lett.2006, 8, 1435.(c) Silva, S.L.; Yaneris, M.-G.; Nagula, S.; Mario, J.S. Synthesis 2011, 51.
[2] (a) Guengeri, F.; Dimari, S.J.; Broquist, H.P.J.Am.Chem.Soc. 1973, 95, 2055.(b) Colegate, S.M.; Dorling, P.R.; Huxtable, C.R.Aust.J.Chem. 1979, 32, 2257.
[3] Liao, Y.F.; Lal, A.; Moremen, K.W.J.Biol.Chem. 1996, 271, 28348.
[4] Shaheen, P.E.; Stadler, W.; Elson, P.; Knox, J.; Winquist, E.; Bukowski, R.M.Invest.New Drugs 2005, 23, 577.
[5] (a) Chou, T.Q.; Jang, C.S.; Fu, F.Y.; Kao, Y.S.; Huang, K.C.Science (Chinese), 1947, 29, 49.(b) Chou, T.-Q.; Fu, F.Y.; Kao, Y.S.J.Am.Chem.Soc.1948, 70, 1765.
[6] Linder, M.R.; Heckeroth, A.R.; Najdrowski, M.; Daugschies, A.; Schollmeyer, D.; Miculkaa, C.Bioorg.Med.Chem.Lett.2007, 17, 4140.
[7] (a) Waletzky, E.; Berkelhammer, G.; Kantor, S.US 3320124, 1967 [Chem.Abstr. 1968, 68, 39647].(b) Elkin, M.; Reich, R.; Nagler, A.; Aingorn, E.; Pines, M.; De Groot, N.; Hochberg, A.; Vlodavsky, I.Clin.Cancer Res. 1999, 5, 1982.
[8] (a) Kobayashi, S.; Ueno, M.; Suzuki, R.; Ishitani, H.Tetrahedron Lett. 1999, 40, 2175.(b) Kobayashi, S.; Ueno, M.; Suzuki, R.; Ishitani, H.; Kim, H.S.; Wataya, Y.J.Org.Chem. 1999, 64, 6833.
[9] For recent asymmetric synthesis, see: (a) Okitsu, O.; Suzuki, R.; Kobayashi, S.Synlett 2000, 989.(b) Takeuchi, Y.; Azuma, K.; Takakura, K.; Abe, H.; Harayama, T.J.Chem.Soc., Chem.Commun. 2000, 1643.(c) Taniguchi, T.; Ogasawara, K.Org.Lett.2000, 2, 3193.(d) Takeuchi, Y.; Azuma, K.; Takakura, K.; Abe, H.; Kim, H.S.; Wataya, Y.; Harayama, T.Tetrahedron 2001, 57, 1213;.(e) Ooi, H.; Urushibara, A.; Esumi, T.; Iwabuchi, Y.; Hatakeyama, S.Org.Lett. 2001, 3, 953.(f) Sugiura, M.; Kobayashi, S.Org.Lett. 2001, 3, 477.(g) Sugiura, M.; Hagio, H.; Hirabayashi, R.; Kobayashi, S.J.Org.Chem. 2001, 66, 809.(h) Sugiura, M.; Hagio, H.; Hirabayashi, R.; Kobayashi, S.J.Am.Chem.Soc.2001, 123, 12510.(i) Huang, P.Q.; Wei, B.G.; Ruan, Y.P.Synlett 2003, 1663.(j) Katoh, M.; Matsune, R.; Nagase, H.; Honda, T.Tetrahedron Lett.2004, 45, 6221.(k) Ashoorzadeh, A.; Caprio, V.Synlett 2005, 346.(l) Takeuchi, Y.; Oshige, M.; Azuma, K.; Abe, H.; Harayama, T.Chem.Pharm.Bull. 2005, 53, 868.(m) Bora, S.; Oscar, L.V.; Veronique, B.; Cossy, J.Synlett 2008, 1216.(n) Sudhakar, N.; Srinivasulu, G.; Rao, G.S.; Rao, B.V.Tetrahedron: Asymmetry 2008, 19, 2153.(o) Wang, R.; Fang, K.; Sun, B.-F.; Xu, M.-H.Lin, G.-Q. Synlett 2009, 2301.(p) Chen, W.; Liebeskind, L.S.J.Am.Chem.Soc.2009, 131, 12546.(q) Ashoorzadeh, A.; Archbald, G.; Caprio, V.Tetrahedron 2009, 65, 4671.(l) Mclaughlin, N.P.; Evans, P.J.Org.Chem. 2010, 75, 518.
[10] Liu, R.-C.; Huang, W.; Ma, J.-Y.; Wei, B.-G.; Lin, G.-Q.Tetrahedron Lett.2009, 50, 4046.
[11] (a) Liu, R.-C.; Wei, J.-H.; Wei, B.-G.; Lin, G.-Q.Tetrahedron: Asymmetry 2008, 19, 2731.(b) Huang, W.-F.; Li, Q.-R.; Chao, L.-M.; Lei, X.-S.; Wei, B.-G.Tetrahedron Lett. 2010, 51, 4317.(c) Huang, W.; Ma, J.-Y.; Yuan, M.; Xu, L.-F.; Wei, B.-G.Tetrahedron 2011, 67, 7829.(d) Wang, X.-L.; Huang, W.-F.; Lei, X.-S.; Wei, B.-G.; Lin, G.-Q.Tetrahedron 2011, 67, 4919.(e) Xarnod, C.; Huang, W.; Ren, R.-G.; Liu, R.-C.; Wei, B.-G.Tetrahedron 2012, 68, 6688.
[12] (a) Jung, M.E; Lyster, M.A.J.Chem.Soc., Chem.Commun. 1978, 7, 315.(b) Bates, R.W.; Dewey, M.R.Org.Lett. 2009, 11, 3706.
[13] Wijdeven, M.A; Botman, P.; Wijtmans.R.Org.Lett. 2005, 7, 4005.
[14] Brown, D.S.; Charreau, P.; Ley, S.V.Tetrahedron 1991, 47, 1311.
Options
文章导航

/

〈 〉