Citation: Xie Xiaojuan, Zhang Zhong, Zhao Huaxin, Wan Wen, Hao Jian. Trifluoromethylated-Imidazolines as Efficient Organocatalyst for Asymmetric Aldol Reaction of Hydroxyacetone with Aldehydes[J]. Chinese Journal of Organic Chemistry, ;2019, 39(1): 117-121. doi: 10.6023/cjoc201809026 shu

Trifluoromethylated-Imidazolines as Efficient Organocatalyst for Asymmetric Aldol Reaction of Hydroxyacetone with Aldehydes

Xie Xiaojuan ^a ,
Zhang Zhong ^a ,
Zhao Huaxin ^a ,
Wan Wen ^a,b,, ,
Hao Jian ^a,b,,

a.
Department of Chemistry, Shanghai University, Shanghai 200444
b.
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Corresponding author: Wan Wen, wanwen@shu.edu.cn Hao Jian, jhao@shu.edu.cn
Received Date: 21 September 2018
Revised Date: 5 December 2018
Available Online: 7 January 2018
Fund Project: the National Natural Science Foundation of China 21572128the National Natural Science Foundation of China 21672139Project supported by the National Natural Science Foundation of China (Nos. 21572128, 21672139) and the Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Science

Figures(2)

Aldol reaction of hydroxyacetone is an all-purpose route to construct the 1, 2-diol building blocks for the synthesis of multifarious natural products and biological active molecules. In this work, a new series of trifluoromethylated-imidazoline organocatalysts have been designed and synthesized. It is found that the trifluoromethylated chiral organocatalyst (2R, 4S)-4-benzyl-1, 2-dimethyl-2-(trifluoromethyl) imidazolidine (1a) has proved to be very efficient for the direct asymmetric aldol reaction of α-hydroxyketones with aldehydes to build the syn-1, 2-diol building blocks. Among the synthesized syn-aldol products, a good yield (up to 96%) and high stereoselectivity (up to dr＝15:1, 99% ee) could be obtained. The F—H bonding derived from trifluoromethyl group was proposed to play an important role in the stabilization of the transition state.
- asymmetric aldol reaction,
- organocatalysis,
- imidazoline,
- trifluoromethyl,
- synthesis
1. [1]
  For reviews, see: (a) Palomo, C.; Oiarbide, M.; Garcia, J. M. Chem. Soc. Rev. 2004, 33, 65.
  (b) Mahrwald, R. Modern Aldol Reactions, Wiley-VCH, Weinheim, Germany, 2004, Vols. 1~2.
  (c) Dalko, P. I.; Moisan, L. Angew. Chem., Int. Ed. 2004, 43, 5138.
  (d) Houk, K. N.; List, B. Acc. Chem. Res. 2004, 37, 487.
  (e) List, B. Chem. Rev. 2007, 107, 5413.
2. [2]
  (a) List, B.; Lerner, R. A. Barbas. C. F. J. Am. Chem. Soc. 2000, 122, 2395.
  (b) Notz, W.; List, B. J. Am. Chem. Soc. 2000, 122, 7386.
3. [3]
  For reviews, see: (a) Torii, H.; Nakadai, M.; Ishihara, K.; Saito, S.; Yamamoto, H. Angew. Chem., Int. Ed. 2004, 43, 1983.
  (b) Northrup, A. B.; Mangion, I. K.; Hettche, F.; MacMillan, D. W. C. Angew. Chem., Int. Ed. 2004, 43, 2152.
  (c) Northrup, A. B.; MacMillan, D. W. C. Science 2004, 305, 1752.
  (d) Cordova, A.; Zou, W.; Ibrahem, I.; Reyes, E.; Engqvist, M.; Liao, W. W. Chem. Commun. 2005, 3586.
  (e) Kano, T.; Takai, J.; Tokuda, O.; Maruoka, K. Angew. Chem., Int. Ed. 2005, 44, 3055.
  (f) Enders, D.; Grondal, C. Angew. Chem., Int. Ed. 2005, 44, 1210.
  (g) Suri, J. T.; Ramachary, D. B.; Barbas. C. F. Org. Lett. 2005, 7, 1383.
  (h) Mase, N.; Nakai, Y.; Ohara, N.; Yoda, H.; Takabe, K.; Tanaka, F.; Barbas. C. F. J. Am. Chem. Soc. 2006, 128, 734.
  (i) Mukherjee, S.; Yang, J. W.; Hoffman, S.; List, B. Chem. Rev. 2007, 107, 5471.
  (j) Li, J.-Y.; Luo, S.-Z.; Cheng, J.-P. J. Org. Chem. 2009, 74, 1747.
  (k) Vellalath, S.; Romo, D. Angew. Chem., Int. Ed. 2016, 55, 13934.
  (l) Frias, M.; Cieslik, W.; Fraile, A.; Rosado-Abon, A.; Garido- Castro, A. F.; Yuste, F.; Aleman, J. Chem.-Eur. J. 2018, 24, 10906.
4. [4]
  For examples of syn-aldol reactions of ketones, see: (a) Ramasastry, S. V.; Zhang, H.; Tanaka, F.; Barbas. C. F. J. Am. Chem. Soc. 2007, 129, 288.
  (b) Luo, S.; Xu, H.; Li, J.; Zhang, L.; Cheng, J.-P. J. Am. Chem. Soc. 2007, 129, 3074.
  (c) Ramasastry, S. S. V.; Albertshofer, K.; Utsumi, N.; Tanaka, F.; Barbas. C. F. Angew. Chem., Int. Ed. 2007, 46, 5572.
  (d) Xu, X.-Y.; Wang, Y.-Z.; Gong, L.-Z. Org. Lett. 2007, 9, 4247.
  (e) Utsumi, N.; Imai, M.; Tanaka, F.; Ramasastry, S. S. V.; Barbas. C. F. Org. Lett. 2007, 9, 3445.
  (f) Ramasastry, S. S. V.; Albertshofer, K.; Utsumi, N.; Barbas. C. F. Org. Lett. 2008, 10, 1621.
  (g) Zhu, M.-K.; Xu, X.-Y.; Gong, L.-Z. Adv. Synth. Catal. 2008, 350, 1390.
  (h) Luo, S.; Xu, H.; Zhang, L.; Li, J.; Cheng, J.-P. Org. Lett. 2008, 10, 653.
5. [5]
6. [6]
  (a) O'Hagan, D.; Bilton, C.; Howard, J. A. K.; Knight, L.; Tozer, D. J. J. Chem. Soc., Perkin Trans. 2 2000, 605.
  (b) Briggs, C. R. S.; O'Hagan, D.; Howard, J. A. K.; Yufit, D. S. J. Fluorine Chem. 2003, 119, 9.
  (c) Gooseman, N. E. J.; O'Hagan, D.; Slawin, A. M. Z.; Teale, A. M.; Tozer, D. J.; Young, R. J. Chem. Commun. 2006, 3190.
  (d) Gooseman, N. E. J.; O'Hagan, D.; Peach, M. G.; Slawin, A. M. Z.; Tozer, D. J.; Young, R. J. Angew. Chem., Int. Ed. 2007, 46, 5904.
  (e) MacMillan, D. W. C. Nature 2008, 455.
  (f) Cahard, D.; Bizet, V. Chem. Soc. Rev. 2014, 43, 135.
7. [7]
  (a) Sparr, C.; Schweizer, W. B.; Senn, H. M.; Gilmou, R. Angew. Chem., Int. Ed. 2009, 48, 3065.
  (b) Diocco, D. A.; Oberg, K. M.; Dalton, D. M.; Rovis. T. J. Am. Chem. Soc. 2009, 131, 10872.
8. [8]
  For reviews, see: (a) List, B.; Shabat, D.; Barbas. C. F.; Lerner, R. A. Chem.-Eur. J. 1999, 4, 881.
  (b) Yoshikawa, N.; Kumagai, N.; Matsunaga, S.; Moll, G.; Ohshima, T.; Suzuki, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2466.
  (c) Trost, B. M.; Ito, H.; Silcoff, E. R. J. Am. Chem. Soc. 2001, 123, 3367.
  (d) Kumagai, N.; Matsunaga, S.; Kinoshita, T.; Harada, S.; Okada, S.; Sakamoto, S.; Yamaguchi, K.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 2169.
9. [9]
  Ahrendt, K. A.; Borths, C. J.; MacMillan. D. W. C. J. Am. Chem. Soc. 2000, 122, 4243. doi: 10.1021/ja000092s
10. [10]
  (a) Sarka, D.; Harman, K.; Ghosh, S.; Headley, D. Tetrahedron: Asymmetry 2011, 22, 1051.
  (b) Czarnecki, P.; Plutecka, A.; Gawronski, J.; Kacprzak, K. Green Chem. 2011, 13, 1280.
  (c) Paradowska, J.; Pasternak, M.; Gut, B.; Gryzło, B.; Mlynarski, J. J. Org. Chem. 2012, 77, 173.
1. [1]
  Yongqing Kuang , Jie Liu , Jianjun Feng , Wen Yang , Shuanglian Cai , Ling Shi . Experimental Design for the Two-Step Synthesis of Paracetamol from 4-Hydroxyacetophenone. University Chemistry, 2024, 39(8): 331-337. doi: 10.12461/PKU.DXHX202403012
2. [2]
  Xinyi Zhang , Kai Ren , Yanning Liu , Zhenyi Gu , Zhixiong Huang , Shuohang Zheng , Xiaotong Wang , Jinzhi Guo , Igor V. Zatovsky , Junming Cao , Xinglong Wu . Progress on Entropy Production Engineering for Electrochemical Catalysis. Acta Physico-Chimica Sinica, 2024, 40(7): 2307057-0. doi: 10.3866/PKU.WHXB202307057
3. [3]
  Jiaming Xu , Yu Xiang , Weisheng Lin , Zhiwei Miao . Research Progress in the Synthesis of Cyclic Organic Compounds Using Bimetallic Relay Catalytic Strategies. University Chemistry, 2024, 39(3): 239-257. doi: 10.3866/PKU.DXHX202309093
4. [4]
  Jing WU , Puzhen HUI , Huilin ZHENG , Pingchuan YUAN , Chunfei WANG , Hui WANG , Xiaoxia GU . Synthesis, crystal structures, and antitumor activities of transition metal complexes incorporating a naphthol-aldehyde Schiff base ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2422-2428. doi: 10.11862/CJIC.20240278
5. [5]
  Xinting XIONG , Zhiqiang XIONG , Panlei XIAO , Xuliang NIE , Xiuying SONG , Xiuguang YI . Synthesis, crystal structures, Hirshfeld surface analysis, and antifungal activity of two complexes Na(Ⅰ)/Cd(Ⅱ) assembled by 5-bromo-2-hydroxybenzoic acid ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1661-1670. doi: 10.11862/CJIC.20240145
6. [6]
  Bin SUN , Heyan JIANG . Glucose-modified bis-Schiff bases: Synthesis and bio-activities in Alzheimer′s disease therapy. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1338-1350. doi: 10.11862/CJIC.20240428
7. [7]
  Lifang HE , Wenjie TANG , Yaoze LUO , Mingsheng LIANG , Jianxin TANG , Yuxuan WU , Fuxing ZHANG , Xiaoming ZHU . Synthesis, structure, and anticancer activity of two dialkyltin complexes constructed based on 2, 2′-bipyridin-6, 6′-dicarboxylic acid. Chinese Journal of Inorganic Chemistry, 2025, 41(8): 1601-1609. doi: 10.11862/CJIC.20250012
8. [8]
  Lei Feng , Ze-Min Zhu , Ying Yang , Zongbin He , Jiafeng Zou , Man-Bo Li , Yan Zhao , Zhikun Wu . Long-Pursued Structure of Au₂₃(S-Adm)₁₆ and the Unexpected Doping Effects. Acta Physico-Chimica Sinica, 2024, 40(5): 2305029-0. doi: 10.3866/PKU.WHXB202305029
9. [9]
  Chunling Qin , Shuang Chen , Hassanien Gomaa , Mohamed A. Shenashen , Sherif A. El-Safty , Qian Liu , Cuihua An , Xijun Liu , Qibo Deng , Ning Hu . Regulating HER and OER Performances of 2D Materials by the External Physical Fields. Acta Physico-Chimica Sinica, 2024, 40(9): 2307059-0. doi: 10.3866/PKU.WHXB202307059
10. [10]
  Dan Liu . 可见光-有机小分子协同催化的不对称自由基反应研究进展. University Chemistry, 2025, 40(6): 118-128. doi: 10.12461/PKU.DXHX202408101
11. [11]
  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
12. [12]
  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
13. [13]
  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
14. [14]
  Wenjie SHI , Fan LU , Mengwei CHEN , Jin WANG , Yingfeng HAN . Synthesis and host-guest properties of imidazolium-functionalized zirconium metal-organic cage. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 105-113. doi: 10.11862/CJIC.20240360
15. [15]
  Yan Kong , Wei Wei , Lekai Xu , Chen Chen . Electrochemical Synthesis of Organonitrogen Compounds from N-integrated CO₂ Reduction Reaction. Acta Physico-Chimica Sinica, 2024, 40(8): 2307049-0. doi: 10.3866/PKU.WHXB202307049
16. [16]
  Lewang Yuan , Yaoyao Peng , Zong-Jie Guan , Yu Fang . Insights into the development of 2D covalent organic frameworks as photocatalysts in organic synthesis. Acta Physico-Chimica Sinica, 2025, 41(8): 100086-0. doi: 10.1016/j.actphy.2025.100086
17. [17]
  Yukun Chang , Haoqin Huang , Baolei Wang . Preparation of Trans-Cinnamic Acid via “One-Pot” Protocol of Aldol Condensation-Hydrolysis Reaction: Recommending an Improved Organic Synthesis Experiment. University Chemistry, 2024, 39(4): 322-328. doi: 10.3866/PKU.DXHX202309095
18. [18]
  Xiaohang JIN , Qi LIU , Jianping LANG . Room‑temperature solid‑state synthesis, structure, and third‑order nonlinear optical properties of phosphine‑ligand‑protected silver thiolate clusters. Chinese Journal of Inorganic Chemistry, 2025, 41(8): 1505-1512. doi: 10.11862/CJIC.20250125
19. [19]
  Hui-Ying Chen , Hao-Lin Zhu , Pei-Qin Liao , Xiao-Ming Chen . Integration of Ru(Ⅱ)-Bipyridyl and Zinc(Ⅱ)-Porphyrin Moieties in a Metal-Organic Framework for Efficient Overall CO₂ Photoreduction. Acta Physico-Chimica Sinica, 2024, 40(4): 2306046-0. doi: 10.3866/PKU.WHXB202306046
20. [20]
  Jiajie Li , Xiaocong Ma , Jufang Zheng , Qiang Wan , Xiaoshun Zhou , Yahao Wang . Recent Advances in In-Situ Raman Spectroscopy for Investigating Electrocatalytic Organic Reaction Mechanisms. University Chemistry, 2025, 40(4): 261-276. doi: 10.12461/PKU.DXHX202406117

Get Citation

PDF

XML

Metrics

PDF Downloads(12)
Abstract views(1273)
HTML views(215)

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