Citation: Zhou Wei, Gao Lihua, Tao Mengna, Su Xiao, Zhao Qingjie, Zhang Junliang. Highly Enantioselective Intermolecular Rauhut–Currier Reaction of Activated Alkenes Catalyzed by Multifunctional Chiral Phosphine[J]. Acta Chimica Sinica, ;2016, 74(10): 800-804. doi: 10.6023/A16070358 shu

Highly Enantioselective Intermolecular Rauhut–Currier Reaction of Activated Alkenes Catalyzed by Multifunctional Chiral Phosphine

Zhou Wei ^a ,
Gao Lihua ^b ,
Tao Mengna ^a ,
Su Xiao ^a ,
Zhao Qingjie ^c,, ,
Zhang Junliang ^a,,

1.
a Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062;
2.
b Jilin Dongfeng Veterinary Pharmacy Factory, Jilin 132011;
3.
c Department of Organic Chemistry, School of Pharmacy, Second Military Medical University, Shanghai 200433

Corresponding author: Zhao Qingjie, Zhang Junliang,
Received Date: 23 July 2016

Fund Project:

The Rauhut-Currier (R-C) reaction, first disclosed by Rauhut and Currier in 1963, is an atom economy strategy for the construction of carbon-carbon bond and a wide range of synthetic valuable building blocks. During the past few decades, significant progress on the enantioselective intramolecular R-C reactions has been achieved by utilizing diverse chiral nucleophilic catalysts such as cysteine derivatives, L-prolinol, hydrogen-bonding catalyst and β-aminephosphine. However, compared to the well-developed enantioselective intramolecular R-C reactions, the enantioselective cross intermolecular R-C reaction concerning two different alkenes has been rarely explored so far. The enantioselective cross R-C reaction still suffers from a series of drawbacks such as low reactivity, enantioselectivity, limited substrate scope and higher catalyst loading. Thus, the development of novel chiral nucleophilic catalyst, for highly enantioselective cross R-C reaction is highly desirable. In this article, we wish to report the application of Xiao-Phos in the highly enantioselective cross intermolecular R-C reaction of vinyl ketone and activated alkenes. Accordingly, a stirred solution of 3-aroyl acrylates 1 (0.2 mmol) and (S,R_S)-X8 (0.02 mmol) in toluene (2 mL) was cooled to -20℃. Subsequently, vinyl ketone 2 (0.4 mmol for aryl vinyl ketone and 0.6 mmol for alkyl vinyl ketone) was added in one portion through a syringe. The mixture was stirred at this temperature until completion of 3-aroyl acrylate as indicated by TLC. After completion of the reaction, the reaction mixture was directly purified by silica gel chromatography to afford the desired RC product. What’s more, control experiments demonstrated that the presence of free sulfinamide N-H in Xiao-Phos is crucial for the enantioselective cross R-C reaction. Finally, for more details about (S,R_S)-X8 in the enantioselective cross R-C reaction, control experiments monitored by ³¹P NMR spectroscopy were conducted and the ³¹P NMR experiments indicated that this cross intermolecular R-C reaction was initiated by the Michael addition of (S,R_S)-X8 to vinyl ketone 2.
- chiral phosphine catalysis,
- Rauhut-Currier reaction,
- 3-aroyl acrylates,
- vinyl ketones,
- nucleophilic catalysis
1. [1]
  [1] Rauhut, M. M.; Currier, H. US 3074999, 1963[Chem. Abstr. 1963, 58, 11224a].
2. [2]
  [2] For selected reviews on the R-C reaction see: (a) Methot, J. L.; Roush, W. R. Adv. Synth. Catal. 2004, 346, 1035; (b) Aroyan, C. E.; Dermenci, A.; Miller, S. J. Tetrahedron 2009, 65, 4069; (c) Xie, P.; Huang, Y. Eur. J. Org. Chem. 2013, 6213; (d) Bharadwaj, K. C. RSC Adv. 2015, 5, 75923.
3. [3]
  [3] For references on the application of the R-C reaction in total synthesis see: (a) Ergüden, J.-K.; Moore, H. W. Org. Lett. 1999, 1, 375; (b) Mergott, D. J.; Frank, S. A.; Roush, W. R. Org. Lett. 2002, 4, 3157; (c) Agapiou, K.; Krische, M. J. Org. Lett. 2003, 5, 1737; (d) Mergott, D. J.; Frank, S. A.; Roush, W. R. Proc. Natl. Acad. Sci. U. S. A. 2004, 101, 11955; (e) Stark, L. M.; Pekari, K.; Sorensen, E. J. Proc. Natl. Acad. Sci. U. S. A. 2004, 101, 12064; (f) Winbush, S. M.; Mergott, D. J.; Roush, W. R. J. Org. Chem. 2008, 73, 1818; (g) Dermenci, A.; Selig, P. S.; Domaoal, R. A.; Spasov, K. A.; Anderson, K. S.; Miller, S. J. Chem. Sci. 2011, 2, 1568.
4. [4]
  [4] For selected progress in the enantioselective intramolecular R-C reaction, see: (a) Aroyan, C. E.; Miller, S. J. J. Am. Chem. Soc. 2007, 129, 256; (b) Aroyan, C. E.; Dermenci, A.; Miller, S. J. J. Org. Chem. 2010, 75, 5784; (c) Osuna, S.; Dermenci, A.; Miller, S. J.; Houk, K. N. Chem. Eur. J. 2013, 19, 14245; (d) Marqués-López, E.; Herrera, R. P.; Marks, T.; Jacobs, W. C.; Könning, D.; de Figueiredo, R. M.; Christmann, M. Org. Lett. 2009, 11, 4116; (e) Wang, X.-F.; Peng, L.; An, J.; Li, C.; Yang, Q.-Q.; Lu, L.-Q.; Gu, F.-L.; Xiao, W.-J. Chem. Eur. J. 2011, 17, 6484; (f) Gong, J.-J.; Li, T.-Z.; Pan, K.; Wu, X.-Y. Chem. Commun. 2011, 47, 1491; (g) Zhang, X.-N.; Shi, M. Eur. J. Org. Chem. 2012, 6271; (h) Takizawa, S.; Nguyen, T. M.-N.; Grossmann, A.; Enders, D.; Sasai, H. Angew. Chem., Int. Ed. 2012, 51, 5423; (i) Takizawa, S.; Nguyen, T. M.-N.; Grossmann, A.; Suzuki, M.; Enders, D.; Sasai, H. Tetrahedron 2013, 69, 1202; (j) Jin, Z.; Yang, R.; Du, Y.; Tiwari, B.; Ganguly, R.; Chi, Y. R. Org. Lett. 2012, 14, 3226; (k) Scanes, R. J. H.; Grossmann, O.; Grossmann, A.; Spring, D. R. Org. Lett. 2015, 17, 2462.
5. [5]
  [5] For selected reports on cross RC reactions see: (a) Jih, R. H.; Hakimelahi, G. H.; Chou, C.-T. Tetrahedron Lett. 1992, 33, 6469; (b) Reynolds, T. E.; Binkley, M. S.; Scheidt, K. A. Org. Lett. 2008, 10, 2449; (c) Kumar, R.; Kumar, T.; Mobin, S. M.; Nambothiri, I. N. N. J. Org. Chem. 2013, 78, 5073; (d) Shanbhag, P.; Nareddy, P. R.; Dadwal, M.; Mobin, S. M.; Namboothiri, I. N. N. Org. Biomol. Chem. 2010, 8, 4867; (e) Zhou, R.; Wang, J.; Yu, J.; He, Z. J. Org. Chem. 2013, 78, 10596.
6. [6]
  [6] For selected reports on domino cyclization initiated by cross R-C reactions see: (a) Sun, X.; Sengupta, S.; Peterson, J. L.; Wang, H.; Lewis, J. P.; Shi, X. Org. Lett. 2007, 9, 4495; (b) Zhong, C.; Chen, Y.; Petersen, J. L.; Akhmedov, N. G.; Shi, X. Angew. Chem., Int. Ed. 2009, 48, 1279; (c) Yao, W.; Wu, Y.; Wang, G.; Zhang, Y.; Ma, C. Angew. Chem., Int. Ed. 2009, 48, 9713; (d) Ma, J.; Xie, P.; Hu, C.; Huang, Y.; Chen, R. Chem. Eur. J. 2011, 17, 7418; (e) Liu, W.; Zhou, J.; Zheng, C.; Chen, X.; Xiao, H.; Yang, Y.; Guo, Y.; Zhao, G. Tetrahedron 2011, 67, 1768; (f) Xie, P.; Huang, Y.; Lai, W.; Meng, X.; Chen, R. Org. Biomol. Chem. 2011, 9, 6707; (g) Shi, Z.; Tong, Q.; Leong, W. W. Y.; Zhong, G. Chem. Eur. J. 2012, 18, 9802; (h) Shi, Z.; Yu, P.; Loh, T.-P.; Zhong, G. Angew. Chem. Int. Ed. 2012, 51, 7825; (i) Hu, C.; Geng, Z.; Ma, J.; Huang, Y.; Chen, R. Chem. Asian J. 2012, 7, 2032; (j) Hu, C.; Zhang, Q.; Huang, Y. Chem. Asian J. 2013, 8, 1981; (k) Shi, Z.; Loh, T.-P. Angew. Chem., Int. Ed. 2013, 52, 8554; (l) Peng, J.; Huang, X.; Zheng, P.-F.; Chen, Y.-C. Org. Lett. 2013, 15, 5534; (m) Zhang, Y.-Y.; Gurubrahamam, R.; Chen, K. Adv. Synth. Catal. 2015, 357, 2457.
7. [7]
  [7] Zhao, Q.-Y.; Pei, C.-K.; Guan, X.-Y.; Shi, M. Adv. Synth. Catal. 2011, 353, 1973.
8. [8]
  [8] Dong, X.; Liang, L.; Li, E.; Huang, Y. Angew. Chem., Int. Ed. 2015, 54, 1621.
9. [9]
  [9] (a) Zhang, Z.-M.; Chen, P.; Li, W.; Niu, Y.; Zhao, X.-L.; Zhang, J. Angew. Chem., Int. Ed. 2014, 53, 4350; (b) Su, X.; Zhou, W.; Li, Y.; Zhang, J. Angew. Chem., Int. Ed. 2015, 54, 6874; (c) Zhou, W.; Su. X.; Tao, M.; Zhu, C.; Zhao, Q.; Zhang, J. Angew. Chem., Int. Ed. 2015, 54, 14853; (d) Chen, P.; Su, X.; W.; Xiao, Y.; Zhang, J. Tetrahedron 2016, 72, 2700; (e) Zhou, W.; Chen, P.; Tao, M.; Su, X.; Zhao, Q.; Zhang, J. Chem. Commun. 2016, 52, 7612; (f) Zhang, Z.-M.; Xu, B.; Xu, S.; Wu, H.-H.; Zhang, J. Angew. Chem., Int. Ed. 2016, 55, 6324; (g) Hu, H.; Wang, Y.; Qian, D.; Zhang, Z.-M.; Liu, L.; Zhang, J. Org. Chem. Front. 2016, 3, 759.
10. [10]
  [10] For reviews related to chiral phosphines catalysis, see: (a) Ye, L.-W.; Zhou, J.; Tang, Y. Chem. Soc. Rev. 2008, 37, 1140; (b) Wei, Y.; Shi, M. Acc. Chem. Res. 2010, 43, 1005; (c) Marinetti, A.; Voituriez, A. Synlett 2010, 174; (d) Wang, S.-X.; Han, X.; Zhong, F.; Wang, Y.; Lu, Y. Synlett 2011, 2766; (e) Zhao, Q.-Y.; Lian, Z.; Wei, Y.; Shi, M. Chem. Commun. 2012, 48, 1724; (f) Xu, L.-W. ChemCatChem 2013, 5, 2775; (g) Wei, Y.; Shi, M. Chem. Rev. 2013, 113, 6659; (h) Fan, Y. C.; Kwon, O. Chem. Commun. 2013, 49, 11588; (i) Wang, Z.; Xu, X.; Kwon, O. Chem. Soc. Rev. 2014, 43, 2927; (j) Wei, Y.; Shi, M. Chem. Asian J. 2014, 9, 2720; (k) Li, W.; Zhang, J. Chem. Soc. Rev. 2016, 45, 1657; (l) Yang, L.; Ma, J. Acta Chim. Sinica 2016, 74, 130(杨丽军, 马军安, 化学学报, 2016, 74, 130.); (m) Zhao, W.-X.; Yang, D.-Y.; Zhang, Y.-H. Chin. J. Org. Chem. 2016, 36, DOI: 10. 6023/ cjoc201603006. (赵文献, 杨代月, 张玉华, 有机化学, 2016, 36, DOI:10.6023/cjoc201603006.)
11. [11]
  [11] For selected asymmetric β-aminephosphine catalysis, see: (a) Fang, Y.-Q.; Jacobsen, E. N. J. Am. Chem. Soc. 2008, 130, 5660; (b) Xiao, H.; Chai, Z.; Zheng, C.-W.; Yang, Y.-Q.; Liu, W.; Zhang, J.-K.; Zhao, G. Angew. Chem., Int. Ed. 2010, 49, 4467; (c) Han, X.; Wang, Y.; Zhong, F.; Lu, Y. J. Am. Chem. Soc. 2011, 133, 1726; (d) Zhong, F.; Luo, J.; Chen, G.-Y.; Dou, X.; Lu, Y. J. Am. Chem. Soc. 2012, 134, 10222; (e) Zhong, F.; Han, X.; Wang, Y.; Lu, Y. Chem. Sci. 2012, 3, 1231; (f) Zhong, F.; Dou, X.; Han, X.; Yao, W.; Zhu, Q.; Meng, Y.; Lu, Y. Angew. Chem., Int. Ed. 2013, 52, 943; (g) Fang, Q.; Tadross, P. M.; Jacobsen, E. N. J. Am. Chem. Soc. 2014, 136, 17966; (h) Han, X.; Yao, W.; Wang, T.; Tan, Y. R.; Yan, Z.; Kwiatkowski, J.; Lu, Y. Angew. Chem., Int. Ed. 2014, 53, 5643. (i) Fang, Y.-Q.; Tadross, P. M.; Jacobsen, E. N. J. Am. Chem. Soc. 2014, 136, 17966; (j) Henry, C. E.; Xu, Q.; Fan, Y. C.; Martin, T. J.; Belding, L.; Dudding, T.; Kwon, O. J. Am. Chem. Soc. 2014, 136, 11890; (k) Yao, W.; Dou, X.; Lu, Y. J. Am. Chem. Soc. 2015, 137, 54; (l) Wang, H.-Y.; Zhang, K.; Zhang, C.-W.; Chai, Z.; Cao, D.-D.; Zhang, J.-X.; Zhao, G. Angew. Chem., Int. Ed. 2015, 54, 1775; (m) Li, Y.; Xiao, S.; Zhou, W.; Li, W.; Zhang, J. Chem. Eur. J. 2015, 21, 4224; (n) Lou, Y.-P.; Zheng, C.-W.; Pang, R.-M.; Jin, Q.-W.; Zhao, G.; Li, Z. Org. Lett. 2015, 17, 688; (o) Wang, T.; Yu, Z.; Hoon, D. L.; Phee, C. Y.; Lan, Y.; Lu, Y. J. Am. Chem. Soc. 2016, 138, 265; (p) Yu, Y.-N.; Xu, M.-H. Acta Chim. Sinica 2014, 72, 815. (余月娜, 徐明华, 化学学报, 2014, 72, 815.); (q) Zheng, S.; Jia, L.; Liu, Z.; Jiang, D.; Huang, Y.; Nong, N.; Zhang, Q.; Shi, J. Chin. J. Org. Chem. 2014, 34, 1840. (郑珊, 贾莉, 刘志森, 蒋达洪, 黄艳仙, 农兰平, 张庆, 施继成, 有机化学, 2014, 34, 1840.).
12. [12]
  [12] (a) Wang, T.; Yao, W.; Zhong, F.; Pang, G. H.; Lu, Y. Angew. Chem., Int. Ed. 2014, 53, 2964; (b) Zhong, F.; Han, X.; Wang, Y.; Lu, Y. Angew. Chem., Int. Ed. 2011, 50, 7837; (c) Han, X.; Zhong, F.; Wang, Y.; Lu, Y. Angew. Chem., Int. Ed. 2012, 51, 767.
13. [13]
  [13] (a) Xia, Y.; Liang, Y.; Chen, Y.; Wang, M.; Jiao, L.; Huang, F.; Liu, S.; Li, Y.; Yu, Z.-X. J. Am. Chem. Soc. 2007, 129, 3470; (b) Huang, G.-T.; Lankau, T.; Yu, C.-H. J. Org. Chem. 2014, 79, 1700.
1. [1]
  Yue Zhao , Yanfei Li , Tao Xiong . Copper Hydride-Catalyzed Nucleophilic Additions of Unsaturated Hydrocarbons to Aldehydes and Ketones. University Chemistry, 2024, 39(4): 280-285. doi: 10.3866/PKU.DXHX202309001
2. [2]
  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
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]
  Lei Shi . Nucleophilicity and Electrophilicity of Radicals. University Chemistry, 2024, 39(11): 131-135. doi: 10.3866/PKU.DXHX202402018
5. [5]
  Guojie Xu , Fang Yu , Yunxia Wang , Meng Sun . Introduction to Metal-Catalyzed β-Carbon Elimination Reaction of Cyclopropenones. University Chemistry, 2024, 39(8): 169-173. doi: 10.3866/PKU.DXHX202401060
6. [6]
  Wentao Lin , Wenfeng Wang , Yaofeng Yuan , Chunfa Xu . Concerted Nucleophilic Aromatic Substitution Reactions. University Chemistry, 2024, 39(6): 226-230. doi: 10.3866/PKU.DXHX202310095
7. [7]
  Zhuoming Liang , Ming Chen , Zhiwen Zheng , Kai Chen . Multidimensional Studies on Ketone-Enol Tautomerism of 1,3-Diketones By ¹H NMR. University Chemistry, 2024, 39(7): 361-367. doi: 10.3866/PKU.DXHX202311029
8. [8]
  Keying Qu , Jie Li , Ziqiu Lai , Kai Chen . Unveiling the Mystery of Chirality from Tartaric Acid. University Chemistry, 2024, 39(9): 369-378. doi: 10.12461/PKU.DXHX202310091
9. [9]
  Tingyu Zhu , Hui Zhang , Wenwei Zhang . Exploration and Practice of Ideological and Political Education in the Course of Experiments on Chemical Functional Molecules: Synthesis and Catalytic Performance Study of Chiral Mn(III)Cl-Salen Complex. University Chemistry, 2024, 39(4): 75-80. doi: 10.3866/PKU.DXHX202311011
10. [10]
  Yan Li , Xinze Wang , Xue Yao , Shouyun Yu . 基于激发态手性铜催化的烯烃E→Z异构的动力学拆分——推荐一个本科生综合化学实验. University Chemistry, 2024, 39(5): 1-10. doi: 10.3866/PKU.DXHX202309053
11. [11]
  Daojuan Cheng , Fang Fang . Exploration and Implementation of Science-Education Integration in Organic Chemistry Teaching for Pharmacy Majors: A Case Study on Nucleophilic Substitution Reactions of Alkyl Halides. University Chemistry, 2024, 39(11): 72-78. doi: 10.12461/PKU.DXHX202403105
12. [12]
  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
13. [13]
  Zhuo WANG , Junshan ZHANG , Shaoyan YANG , Lingyan ZHOU , Yedi LI , Yuanpei LAN . Preparation and photocatalytic performance of CeO₂-reduced graphene oxide by thermal decomposition. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1708-1718. doi: 10.11862/CJIC.20240067
14. [14]
  Zhuoyan Lv , Yangming Ding , Leilei Kang , Lin Li , Xiao Yan Liu , Aiqin Wang , Tao Zhang . Light-Enhanced Direct Epoxidation of Propylene by Molecular Oxygen over CuO_x/TiO₂ Catalyst. Acta Physico-Chimica Sinica, 2025, 41(4): 100038-. doi: 10.3866/PKU.WHXB202408015
15. [15]
  Linjie ZHU , Xufeng LIU . Electrocatalytic hydrogen evolution performance of tetra-iron complexes with bridging diphosphine ligands. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 321-328. doi: 10.11862/CJIC.20240207
16. [16]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
17. [17]
  Yurong Tang , Yunren Shi , Yi Xu , Bo Qin , Yanqin Xu , Yunfei Cai . Innovative Experiment and Course Transformation Practice of Visible-Light-Mediated Photocatalytic Synthesis of Isoquinolinone. University Chemistry, 2024, 39(5): 296-306. doi: 10.3866/PKU.DXHX202311087
18. [18]
  Xingyang LI , Tianju LIU , Yang GAO , Dandan ZHANG , Yong ZHOU , Meng PAN . A superior methanol-to-propylene catalyst: Construction via synergistic regulation of pore structure and acidic property of high-silica ZSM-5 zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1279-1289. doi: 10.11862/CJIC.20240026
19. [19]
  Yinuo Wang , Siran Wang , Yilong Zhao , Dazhen Xu . Selective Synthesis of Diarylmethyl Anilines and Triarylmethanes via Multicomponent Reactions: Introduce a Comprehensive Experiment of Organic Chemistry. University Chemistry, 2024, 39(8): 324-330. doi: 10.3866/PKU.DXHX202401063
20. [20]
  .
  CCS Chemistry | 超分子活化底物为自由基促进高效选择性光催化氧化
  . CCS Chemistry, 2025, 7(10.31635/ccschem.025.202405229): -.

Get Citation

PDF

XML

Metrics

PDF Downloads(11)
Abstract views(858)
HTML views(101)

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