Enantioselective N-propargylation of indoles via Cu-catalyzed propargylic alkylation/dehydrogenation of indolines

doi:10.1016/S1872-2067(14)60230-8

Abstract

Abstract:

The synthesis of optically active N-propargylindoles has been accomplished via the Cu-catalyzed asymmetric propargylic alkylation of indolines with propargylic esters, followed by the dehydrogenation of the resulting N-substituted indolines with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone. The reaction proceeded in good yield with high enantioselectivity under mild conditions using a bulky and structurally rigid tridentate ketimine P,N,N-ligand, and exhibited a broad substrate scope.

Key words: Asymmetric synthesis, Copper, Propargylic substitution, Dehydrogenation, N-propargylindole

Fulin Zhu, Xiangping Hu. Enantioselective N-propargylation of indoles via Cu-catalyzed propargylic alkylation/dehydrogenation of indolines[J]. Chinese Journal of Catalysis, 2015, 36(1): 86-92.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(14)60230-8

https://www.cjcatal.com/EN/Y2015/V36/I1/86

References

[1] Hattori G, Matsuzawa H, Miyake Y, Nishibayashi Y. Angew Chem Int Ed, 2008, 47: 3781
[2] Detz R J, Delville M M E, Hiemstra H, van Maarseveen J H. Angew Chem Int Ed, 2008, 47: 3777
[3] Nishibayashi Y. Synthesis, 2012, 44: 489
[4] Ding C H, Hou X L. Chem Rev, 2011, 111: 1914
[5] Fang P, Hou X L. Org Lett, 2009, 11: 4612
[6] Hattori G, Yoshida A, Miyake Y, Nishibayashi Y. J Org Chem, 2009, 74: 7603
[7] Hattori G, Miyake Y, Nishibayashi Y. ChemCatChem, 2010, 2: 155
[8] Hattori G, Sakata K, Matsuzawa H, Tanabe Y, Miyake Y, Nishibayashi Y. J Am Chem Soc, 2010, 132: 10592
[9] Detz R J, Abiri Z, le Griel R, Hiemstra H, van Maarseveen J H. Chem Eur J, 2011, 17: 5921
[10] Yoshida A, Ikeda M, Hattori G, Miyake Y, Nishibayashi Y. Org Lett, 2011, 13: 592
[11] Yoshida A, Hattori G, Miyake Y, Nishibayashi Y. Org Lett, 2011, 13: 2460
[12] Zhang C, Wang Y H, Hu X H, Zheng Z, Xu J, Hu X P. Adv Synth Catal, 2012, 354: 2854
[13] Zhang C, Hu X H, Wang Y H, Zheng Z, Xu J, Hu X P. J Am Chem Soc, 2012, 134: 9585
[14] Mino T, Taguchi H, Hashimoto M, Sakamoto M. Tetrahedron: Asymmetry, 2013, 24: 1520
[15] Han F Z, Zhu F L, Wang Y H, Zou Y, Hu X H, Chen S, Hu X P. Org Lett, 2014, 16: 588
[16] Zhu F L, Zou Y, Zhang D Y, Wang Y H, Hu X H, Chen S, Xu J, Hu X P. Angew Chem Int Ed, 2014, 53: 1410
[17] Zou Y, Zhu F L, Duan Z C, Wang Y H, Zhang D Y, Cao Z, Zheng Z, Hu X P. Tetrahedron Lett, 2014, 55: 2033
[18] Shibata M, Nakajima K, Nishibayashi Y. Chem Commun, 2014, 50: 7874
[19] Zhu F L, Wang Y H, Zhang D Y, Hu X H, Chen S, Hou C J, Xu J, Hu X P. Adv Synth Catal, 2014, 356: 3231
[20] Zhu F L, Wang Y H, Zhang D Y, Xu J, Hu X P. Angew Chem Int Ed, 2014, 53: 10223
[21] Zhang D Y, Zhu F L, Wang Y H, Hu X H, Chen S, Hou C J, Hu X P. Chem Commun, 2014, 50: 14459
[22] Bandini M, Umani-Ronchi A. Catalytic Asymmetric Friedel-Crafts Alkylations. Weinheim: Wiley-VCH, 2009
[23] Baran P S, Guerrero C A, Corey E J. J Am Chem Soc, 2003, 125: 5628
[24] Hayashi H, Takiuchi K, Murao S, Arai M. Agric Biol Chem, 1989, 53: 461
[25] Liu W B, Zhang X, Dai L X, You S L. Angew Chem Int Ed, 2012, 51: 5183
[26] Galm U, Hager M H, van Lanen S G, Ju J H, Thorson J S, Shen B. Chem Rev, 2005, 105: 739