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

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

Fulin Zhu ^a,b ,
Xiangping Hu ^a,,

1.
a Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;

Corresponding author: Xiangping Hu,
Received Date: 30 August 2014
Available Online: 19 September 2014
Fund Project:

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.
- Asymmetric synthesis,
- Copper,
- Propargylic substitution,
- Dehydrogenation,
- N-propargylindole
1. [1]
  [1] Hattori G, Matsuzawa H, Miyake Y, Nishibayashi Y. Angew Chem Int Ed, 2008, 47: 3781
2. [2]
  [2] Detz R J, Delville M M E, Hiemstra H, van Maarseveen J H. Angew Chem Int Ed, 2008, 47: 3777
3. [3]
  [3] Nishibayashi Y. Synthesis, 2012, 44: 489
4. [4]
  [4] Ding C H, Hou X L. Chem Rev, 2011, 111: 1914
5. [5]
  [5] Fang P, Hou X L. Org Lett, 2009, 11: 4612
6. [6]
  [6] Hattori G, Yoshida A, Miyake Y, Nishibayashi Y. J Org Chem, 2009, 74: 7603
7. [7]
  [7] Hattori G, Miyake Y, Nishibayashi Y. ChemCatChem, 2010, 2: 155
8. [8]
  [8] Hattori G, Sakata K, Matsuzawa H, Tanabe Y, Miyake Y, Nishibayashi Y. J Am Chem Soc, 2010, 132: 10592
9. [9]
  [9] Detz R J, Abiri Z, le Griel R, Hiemstra H, van Maarseveen J H. Chem Eur J, 2011, 17: 5921
10. [10]
  [10] Yoshida A, Ikeda M, Hattori G, Miyake Y, Nishibayashi Y. Org Lett, 2011, 13: 592
11. [11]
  [11] Yoshida A, Hattori G, Miyake Y, Nishibayashi Y. Org Lett, 2011, 13: 2460
12. [12]
  [12] Zhang C, Wang Y H, Hu X H, Zheng Z, Xu J, Hu X P. Adv Synth Catal, 2012, 354: 2854
13. [13]
  [13] Zhang C, Hu X H, Wang Y H, Zheng Z, Xu J, Hu X P. J Am Chem Soc, 2012, 134: 9585
14. [14]
  [14] Mino T, Taguchi H, Hashimoto M, Sakamoto M. Tetrahedron: Asymmetry, 2013, 24: 1520
15. [15]
  [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. [16]
  [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. [17]
  [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. [18]
  [18] Shibata M, Nakajima K, Nishibayashi Y. Chem Commun, 2014, 50: 7874
19. [19]
  [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. [20]
  [20] Zhu F L, Wang Y H, Zhang D Y, Xu J, Hu X P. Angew Chem Int Ed, 2014, 53: 10223
21. [21]
  [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. [22]
  [22] Bandini M, Umani-Ronchi A. Catalytic Asymmetric Friedel-Crafts Alkylations. Weinheim: Wiley-VCH, 2009
23. [23]
  [23] Baran P S, Guerrero C A, Corey E J. J Am Chem Soc, 2003, 125: 5628
24. [24]
  [24] Hayashi H, Takiuchi K, Murao S, Arai M. Agric Biol Chem, 1989, 53: 461
25. [25]
  [25] Liu W B, Zhang X, Dai L X, You S L. Angew Chem Int Ed, 2012, 51: 5183
26. [26]
  [26] Galm U, Hager M H, van Lanen S G, Ju J H, Thorson J S, Shen B. Chem Rev, 2005, 105: 739
1. [1]
  Renxiao Liang , Zhe Zhong , Zhangling Jin , Lijuan Shi , Yixia Jia . A Palladium/Chiral Phosphoric Acid Relay Catalysis for the One-Pot Three-Step Synthesis of Chiral Tetrahydroquinoline. University Chemistry, 2024, 39(5): 209-217. doi: 10.3866/PKU.DXHX202311024
2. [2]
  Hong Lu , Yidie Zhai , Xingxing Cheng , Yujia Gao , Qing Wei , Hao Wei . Advancements and Expansions in the Proline-Catalyzed Asymmetric Aldol Reaction. University Chemistry, 2024, 39(5): 154-162. doi: 10.3866/PKU.DXHX202310074
3. [3]
  Ke QIAO , Yanlin LI , Shengli HUANG , Guoyu YANG . Advancements in asymmetric catalysis employing chiral iridium (ruthenium) complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2091-2104. doi: 10.11862/CJIC.20240265
4. [4]
  Chen LU , Qinlong HONG , Haixia ZHANG , Jian ZHANG . Syntheses, structures, and properties of copper-iodine cluster-based boron imidazolate framework materials. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 149-154. doi: 10.11862/CJIC.20240407
5. [5]
  Qianwen Han , Tenglong Zhu , Qiuqiu Lü , Mahong Yu , Qin Zhong . 氢电极支撑可逆固体氧化物电池性能及电化学不对称性优化. Acta Physico-Chimica Sinica, 2025, 41(1): 2309037-. doi: 10.3866/PKU.WHXB202309037
6. [6]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
7. [7]
  Ping Song , Nan Zhang , Jie Wang , Rui Yan , Zhiqiang Wang , Yingxue Jin . Experimental Teaching Design on Synthesis and Antitumor Activity Study of Cu-Pyropheophorbide-a Methyl Ester. University Chemistry, 2024, 39(6): 278-286. doi: 10.3866/PKU.DXHX202310087
8. [8]
  Cheng Zheng , Shiying Zheng , Yanping Zhang , Shoutian Zheng , Qiaohua Wei . Synthesis, Copper Content Analysis, and Luminescent Performance Study of Binuclear Copper (I) Complexes with Isomeric Luminescence Shift: A Comprehensive Chemical Experiment Recommendation. University Chemistry, 2024, 39(7): 322-329. doi: 10.3866/PKU.DXHX202310131
9. [9]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
10. [10]
  Tingbo Wang , Yao Luo , Bingyan Hu , Ruiyuan Liu , Jing Miao , Huizhe Lu . Quantitative Computational Study on the Claisen Rearrangement Reaction of Allyl Phenyl Ethers: An Introduction to a Computational Chemistry Experiment. University Chemistry, 2024, 39(11): 278-285. doi: 10.12461/PKU.DXHX202403082
11. [11]
  Pei Li , Yuenan Zheng , Zhankai Liu , An-Hui Lu . Boron-Containing MFI Zeolite: Microstructure Control and Its Performance of Propane Oxidative Dehydrogenation. Acta Physico-Chimica Sinica, 2025, 41(4): 100034-. doi: 10.3866/PKU.WHXB202406012
12. [12]
  Xuejie Wang , Guoqing Cui , Congkai Wang , Yang Yang , Guiyuan Jiang , Chunming Xu . 碳基催化剂催化有机液体氢载体脱氢研究进展. Acta Physico-Chimica Sinica, 2025, 41(5): 100044-. doi: 10.1016/j.actphy.2024.100044
13. [13]
  Dongheng WANG , Si LI , Shuangquan ZANG . Construction of chiral alkynyl silver chains and modulation of chiral optical properties. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 131-140. doi: 10.11862/CJIC.20240379
14. [14]
  Jiapei Zou , Junyang Zhang , Xuming Wu , Cong Wei , Simin Fang , Yuxi Wang . A Comprehensive Experiment Based on Electrocatalytic Nitrate Reduction into Ammonia: Synthesis, Characterization, Performance Exploration, and Applicable Design of Copper-based Catalysts. University Chemistry, 2024, 39(6): 373-382. doi: 10.3866/PKU.DXHX202312081
15. [15]
  Xiaofeng Xia , Jielian Zhu . Innovative Comprehensive Experimental Design: Synthesis of 6-Fluoro-N-benzoyl Tetrahydroquinoline. University Chemistry, 2024, 39(10): 344-352. doi: 10.12461/PKU.DXHX202405063
16. [16]
  Zhengyu Zhou , Huiqin Yao , Youlin Wu , Teng Li , Noritatsu Tsubaki , Zhiliang Jin . Synergistic Effect of Cu-Graphdiyne/Transition Bimetallic Tungstate Formed S-Scheme Heterojunction for Enhanced Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2024, 40(10): 2312010-. doi: 10.3866/PKU.WHXB202312010
17. [17]
  Lirui Shen , Kun Liu , Ying Yang , Dongwan Li , Wengui Chang . Synthesis and Application of Decanedioic Acid-N-Hydroxysuccinimide Ester: Exploration of Teaching Reform in Comprehensive Applied Chemistry Experiment. University Chemistry, 2024, 39(8): 212-220. doi: 10.3866/PKU.DXHX202312035
18. [18]
  Qiaowen CHANG , Ke ZHANG , Guangying HUANG , Nuonan LI , Weiping LIU , Fuquan BAI , Caixian YAN , Yangyang FENG , Chuan ZUO . Syntheses, structures, and photo-physical properties of iridium phosphorescent complexes with phenylpyridine derivatives bearing different substituting groups. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 235-244. doi: 10.11862/CJIC.20240311
19. [19]
  Hong LI , Xiaoying DING , Cihang LIU , Jinghan ZHANG , Yanying RAO . Detection of iron and copper ions based on gold nanorod etching colorimetry. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 953-962. doi: 10.11862/CJIC.20230370
20. [20]
  Ji Qi , Jianan Zhu , Yanxu Zhang , Jiahao Yang , Chunting Zhang . Visible Color Change of Copper (II) Complexes in Reversible SCSC Transformation: The Effect of Structure on Color. University Chemistry, 2024, 39(3): 43-57. doi: 10.3866/PKU.DXHX202307050

Get Citation

PDF

XML

Metrics

PDF Downloads(161)
Abstract views(486)
HTML views(14)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142