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

doi:10.6023/cjoc201809026

Chin. J. Org. Chem. ›› 2019, Vol. 39 ›› Issue (1): 117-121.DOI: 10.6023/cjoc201809026 Previous Articles Next Articles

Special Issue: 庆祝陈庆云院士九十华诞

Articles

含氟咪唑啉型有机催化剂在不对称Aldol反应中的研究

解晓娟^a, 张忠^a, 赵华欣^a, 万文^a,b, 郝健^a,b

a 上海大学化学系上海 200444;
b 中国科学院上海有机化学研究所有机氟化学重点实验室上海 200032

收稿日期:2018-09-21 修回日期:2018-12-05 发布日期:2018-12-07
通讯作者: 万文, 郝健 E-mail:wanwen@shu.edu.cn;jhao@shu.edu.cn
基金资助:
国家自然科学基金基（Nos.21572128，21672139）及中国科学院上海有机化学研究所氟重点实验室开放基金资助项目.

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

Received:2018-09-21 Revised:2018-12-05 Published:2018-12-07
Contact: 10.6023/cjoc201809026 E-mail:wanwen@shu.edu.cn;jhao@shu.edu.cn
Supported by:
Project 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.

1. Trifluoromethylated-Imidazolines as Efficient Organocatalyst for Asymmetric Aldol Reaction of Hydroxyacetone with Aldehydes.PDF(2417KB)

Abstract

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.

Key words: asymmetric aldol reaction, organocatalysis, imidazoline, trifluoromethyl, synthesis

Cite this article

Xie Xiaojuan, Zhang Zhong, Zhao Huaxin, Wan Wen, Hao Jian. Trifluoromethylated-Imidazolines as Efficient Organocatalyst for Asymmetric Aldol Reaction of Hydroxyacetone with Aldehydes[J]. Chin. J. Org. Chem., 2019, 39(1): 117-121.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[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] (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] 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] 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] (a) Purser, S.; Moore, P. R.; Swallow S.; Gouverneur, V. Chem. Soc. Rev. 2008, 37, 320.
(b) Begue, J. P.; Bonnet-Delpon, D. Bioorganic and Medicinal Chemistry of Fluorine, Wiley, Hoboken, 2008.
(c) Ojima, I. Fluorine in Medicinal Chemistry and Chemical Biology, John Wiley & Sons, Chichester, 2009.
(d) Wan, W.; Ma, G.; Li, J.; Chen, Y.; Hu, Q.; Li, M.; Jiang, H.; Deng, H.; Hao, J. Chem. Commun. 2016, 52, 1598.
(e) Wang, J.; Sanchez-Rosello, M.; Acena J.; Sorochinsky, A. E.; Fustero, S.; Soloshonok, V. A.; Liu, H. Chem. Rev. 2014, 114, 2432.
(f) Lee, K. A.; Silverio, D. L.; Torker, S.; Robbins, D. W.; Haeffner, F.; Mei, F. W.; Hoveyda, A. H. Nat. Chem. 2016, 8, 768.
(g) Rong, J.; Ni, C.; Wang, Y.; Kuang, C.; Gu, Y.; Hu, J. Acta Chim. Sinica 2017, 75, 105(in Chinese). (荣健, 倪传法, 王云泽, 匡翠文, 顾玉诚, 胡金波, 化学学报, 2017, 75, 105.)
(h) Xu, X.; Chen, H.; He, J.; Xu, H. Chin. J. Chem. 2017, 35, 1665.
(i) Hui, R.; Zhang, S.; Tan, Z.; Wu, X.; Feng, B. Chin. J. Org. Chem. 2017, 37, 3060(in Chinese). (惠人杰, 张士伟, 谭政, 吴小培, 冯柏年, 有机化学, 2017, 37, 3060.)
[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] (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] 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] Ahrendt, K. A.; Borths, C. J.; MacMillan. D. W. C. J. Am. Chem. Soc. 2000, 122, 4243.
[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.; Gryzlo, B.; Mlynarski, J. J. Org. Chem. 2012, 77, 173.

[1]	Fakai Zou, Nengzhong Wang, Hui Yao, Hui Wang, Mingguo Liu, Nianyu Huang. Regio- and Stereo-selective Synthesis of 1β-/3R-Aryl Thiosugar [J]. Chinese Journal of Organic Chemistry, 2024, 44(2): 593-604.
[2]	Luyao Li, Zhongwen He, Zhenguo Zhang, Zhenhua Jia, Teck-Peng Loh. Application of Triaryl Carbenium in Organic Synthesis [J]. Chinese Journal of Organic Chemistry, 2024, 44(2): 421-437.
[3]	Qinggang Mei, Qinghan Li. Recent Progress of Visible Light-Induced the Synthesis of C(3) (Hetero)arylthio Indole Compounds [J]. Chinese Journal of Organic Chemistry, 2024, 44(2): 398-408.
[4]	Penghui Li, Qingyang Xie, Fuxian Wan, Yuanhong Zhang, Lin Jiang. Synthesis and Fungicidal Activity of Novel Substituted Pyrimidine-5-carboxamides Bearing Cyclopropyl Moiety [J]. Chinese Journal of Organic Chemistry, 2024, 44(2): 650-656.
[5]	Weiqing Yang, Yanbing Ge, Yuanyuan Chen, Ping Liu, Haiyan Fu, Menglin Ma. Design and Synthesis of Fluorescent 1,8-Napthalimide Derivatives and Their Identification of Cysteine [J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 180-194.
[6]	Si Wen, Yuhao Ding, Qingyu Tian, Jin Ge, Guolin Cheng. Rhodium(III)-Catalyzed Synthesis of CF₃-1H-benzo[de][1,8]naph-thyridines via C—H Activation/Annulation of Benzimidates and CF₃-Imidoyl Sulfoxonium Ylides [J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 291-300.
[7]	Qianfan Zhao, Yongzheng Chen, Shiming Zhang. Application and Mechanism Study of Carbon-Based Metal-Free Catalysts in Organic Synthesis [J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 137-147.
[8]	Shan Chen, Zhilin Chen, Qiong Hu, Yanshuang Meng, Yue Huang, Pingfang Tao, Liru Lu, Guobao Huang. Recognition of Bis-thiourea Tweezers to Neutral Molecules in Non-Polar Solvent [J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 277-281.
[9]	Huakun Wang, Xiaolong Ren, Yining Xuan. Study of the Halide Salt Catalyzed [3＋2] Cycloaddition of α,β-Epoxy Carboxylate with Isocyanate [J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 251-258.
[10]	Yukun Jin, Baoyi Ren, Fushun Liang. Visible Light-Mediated Selective C—F Bond Cleavage of Trifluoromethyl Groups and Its Application in Synthesizing gem-Difluoro-Containing Compounds [J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 85-110.
[11]	Cuiyun Ma, Hailan Luo, Fuhua Zhang, Dan Guo, Shuxing Chen, Fei Wang. Green Biosynthesis, Photophysical Properties and Application of 3-Pyrrolyl BODIPY [J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 216-223.
[12]	Bozhen Wang, Jie Zhang, Chunhui Nian, Mingming Jin, Miaomiao Kong, Wulan Li, Wenfei He, Jianzhang Wu. Synthesis and Antitumor Activity of 3,4-Dichlorophenyl Amides [J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 232-241.
[13]	Shihang Yu, Jiawei Liu, Biyu An, Qinghua Bian, Min Wang, Jiangchun Zhong. Asymmetric Synthesis of the Contact Sex Pheromone of Neoclytus acuminatus acuminatus (Fabricius) [J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 301-308.
[14]	Yang Li, Jinding Yuan, Di Zhao. Deep Eutectic Solvent of 1,3-Dimethylurea/L-(+)-Tartaric Acid for the Green Synthesis of (E)-2-Styrylquinoline-3-carboxylic Acid Derivatives [J]. Chinese Journal of Organic Chemistry, 2023, 43(9): 3268-3276.
[15]	Dandan Sui, Nannan Cen, Ruoqu Gong, Yang Chen, Wenbo Chen. Supporting-Electrolyte-Free Electrochemical Synthesis of Trifluoromethylated Oxindoles in Continuous Flow [J]. Chinese Journal of Organic Chemistry, 2023, 43(9): 3239-3245.

含氟咪唑啉型有机催化剂在不对称Aldol反应中的研究

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

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments