BINOL双酰胺绿色催化吲哚与硝基烯烃的Friedel-Crafts烷基化反应
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摘要
合成了3种BINOL双酰胺(Ⅰ～Ⅲ),其结构经~1H NMR,~(13)C NMR, HR-MS(ESI)和元素分析确证。研究了I～III对取代吲哚和硝基烯烃的Friedel-Crafts烷基化反应的催化性能,并对反应条件进行了优化。结果表明:在最优条件(CH_2Cl_2为溶剂,Ⅰ为催化剂,于40℃反应12 h)下,吲哚及取代吲哚与硝基烯烃均能有效的进行Friedel-Crafts烷基化反应,收率和ee值最高可达88%和90%。
Three BINOL bisamides(Ⅰ～Ⅲ) were synthesized and the structures were confirmed by ~1H NMR, ~(13)C NMR, HR-MS(ESI) and elemental analysis. The catalytic properties of I～III were investigated using the Friedel-Crafts alkylation of substituted indoles with nitroolefins as the template reaction. And the reaction conditions were optimized. The results showed that under the optimized condition(CH_2Cl_2 as the solvent, Ⅰ as the catalyst, reaction at 40 ℃ for 12 h), the Friedel-Crafts alkylation reaction undergo efficiently and the yield and ee were up to 88% and 90%, respectively.
Three BINOL bisamides(Ⅰ～Ⅲ) were synthesized and the structures were confirmed by ~1H NMR, ~(13)C NMR, HR-MS(ESI) and elemental analysis. The catalytic properties of I～III were investigated using the Friedel-Crafts alkylation of substituted indoles with nitroolefins as the template reaction. And the reaction conditions were optimized. The results showed that under the optimized condition(CH_2Cl_2 as the solvent, Ⅰ as the catalyst, reaction at 40 ℃ for 12 h), the Friedel-Crafts alkylation reaction undergo efficiently and the yield and ee were up to 88% and 90%, respectively.
引文
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[2] OLLIS D F, EKABI H A. Photocatalytic Purification and Treatment of Water and Air[M].Elsevier Science,1993.
[3] LIN J H, XIAO J C. The Asymmetric Friedel-Crafts reaction of indoles with fluoroalkylated nitroalkenes catalyzed by chiral phosphoric acid[J].Eur J Org Chem,2011,2011(45):4536-4539.
[4] WAHED A R, NORBERT M T, TESUYA. Process for the Preparation of Pyrrolines From Gamma-nitroketones Use of the Gamma-nitroketones As Pesticidal Agents[M].PCT Int Appl,2011.
[5] GAO J R, WU H, XIANG B, et al. Highly enantioselective construction of trifluoromethylated all-carbon quaternary stereocenters via nickel-catalyzed Friedel Crafts alkylation reaction[J].J Am Chem Soc2013,135(8):2983-2986.
[6] SINGH P K, BISAI A, SINGH V K. Enantioselective Friedel-Crafts alkylation of indoles with nitroalkenes catalyzed by a bis(oxazoline)-Cu(II) complex[J].Cheminform,2007,48(7):1127-1129.
[7] NING N W, YONG L Y, WEN P W, et al. Friedel-Crafts alkylatio nofindoles with nitroalkenes catalyzed by Cu(Ⅱ)-iminecomplex[J].Chinese Chemical Letters,2011,43(10):1155-1158.
[8] LU S F, DU D M, XU J. Enantioselective Friedel-Crafts alkylation of indoles with nitroalkenes catalyzed by bifunctional tridentate bis(oxazoline)-Zn(II) complex[J].Organic Letters,2006,37(37):2115-2118.
[9] HERRERA R P, SGARZANI V, BERNARDI L, et al. Catalytic enantioselective Friedel-Crafts alkylation of indoles with nitroalkenes by using a simple thiourea organocatalyst[J].Angewandte Chemie International Edition,2005,44(40):6576-6579.
[10] FLEMING E M, MCCABE T, CONNON S J. Novel axially chiral bis-arylthiourea-based organocatalysts for asymmetric Friedel-Crafts type reactions[J].Cheminform,2006,38(47):7037-7042.
[11] SHENG Y F, LI G Q, KANG Q, et al. Asymmetric Friedel-Crafts reaction of 4,7-dihydroindoles with nitroolefins by chiral Br?nsted acids under low catalyst loading[J].Chemistry,2009,15(14):3351-3354.
[12] ITOH J, FUCHIBE K, AKIYAMA T. Chiral phosphoric acid catalyzed enantioselective Friedel-Crafts alkylation of indoles with nitroalkenes:Cooperative effect of 3 a molecular sieves[J].Angewandte Chemie,2008,47(21):4016-4018.
[13] ZHUANG W, HAZELL R G, JOERGENSEN K A. Enantioselective Friedel-Crafts type addition of indoles to nitro-olefins using achiral hydrogen-bonding catalyst-synthesis of optically active tetrahydro-β-carbolines[J].Organic & biomolecular chemistry,2005,3(14):2566.
[14] XIE J W, ZHU X H, HUANG M N, et al. Sc(OTf)3:A highly efficient and renewable catalyst for Michael addition of indoles to nitroolefins in water[J].Syn Comm,2009,42(21):3259-3267.
[15] LU S F, DU D M, XU J X. Enantioselective Friedel-Crafts alkylation of indoles with nitroalkenes catalyzed by bifunctional tridentate bis(oxazoline)-Zn(II) complex[J].Org Let,2006,8(10):2115-2118.
[16] PATELIYA M H, VEERABABURAO K, CHUN W K. Catalyst-free aqueous-mediated conjugative addition of indoles to β-nitrostyrenes[J].Cheminform,2009,40(11):7005-7007.
[17] LIN C, HSU J, SASTRY M N V, et al. I2-catalyzed Michael addition of indole and pyrrole to nitroolefins[J].Tetrahedron,2005,61(49):11751-11757.