Citation: Wu Qiong, Zhao Jiajia, Sun Sibing, Tu Mansu, Shi Feng. Catalytic Asymmetric[4+2] Cycloaddition of o-Hydroxybenzyl Alcohols with o-Hydroxyl Styrenes: Diastereo-and Enantioselective Construction of Chiral Chroman Scaffold[J]. Acta Chimica Sinica, ;2016, 74(7): 576-581. doi: 10.6023/A16020080 shu

Catalytic Asymmetric[4+2] Cycloaddition of o-Hydroxybenzyl Alcohols with o-Hydroxyl Styrenes: Diastereo-and Enantioselective Construction of Chiral Chroman Scaffold

Wu Qiong ^a,b ,
Zhao Jiajia ^a ,
Sun Sibing ^a ,
Tu Mansu ^a,*,, ,
Shi Feng ^a,*,,

a.
School of Chemistry and Chemical Engineering, and the Key Laboratory of Biotechnology for Medicinal Plant of Jiangsu Province, Jiangsu Normal University, Xuzhou 221116
b.
School of Chemistry and Chemical Engineering, Xuzhou Institute of Technology, Xuzhou 221111

Corresponding author: Tu Mansu, Shi Feng, fshi@jsnu.edu.cn
Received Date: 5 February 2016

Fund Project: the National Natural Science Foundation of China 21232007the National Natural Science Foundation of China 21372002

Figures(6)

A chiral phosphoric acid-catalyzed asymmetric[4+2] cycloaddition of o-hydroxyl styrenes with o-quinone methides (o-QMs) generated in situ from o-hydroxybenzyl alcohols has been established. O-Hydroxybenzyl alcohols could transform into o-QM intermediates under the catalysis of chiral phosphoric acid (CPA), which are easily activated by CPA via hydrogen-bonding interaction. On the other hand, o-hydroxyl styrenes could also be activated by CPA via forming a hydrogen bond between the hydroxyl group of styrenes and the phosphoryl oxygen of CPA. So, by selecting o-hydroxybenzyl alcohols as precursors of dienes and o-hydroxyl styrenes as dienophiles under the catalysis of CPA, this catalytic asymmetric[4+2] cycloaddition provided an efficient strategy for constructing enantioenriched chroman framework with two stereogenic centers. A variety of substituted o-hydroxybenzyl alcohols and o-hydroxyl styrenes bearing either electron-donating or electron-withdrawing groups could be applicable to the reaction, delivering chiral chroman derivatives in high yields, considerable enantioselectivities and excellent diastereoselectivities (up to 78% yield, 72% ee, most of examples > 95:5 dr). The electronic nature of the substituents has some effect on the reaction. Namely, the electron-donating groups were beneficial to both the reactivity and the enantioselectivity. Based on the control experiments, it is suggested that the o-hydroxyl styrenes and the o-QM intermediates generated from o-hydroxybenzyl alcohols were simultaneously activated by CPA via forming double hydrogen bonds, thus facilitating the reaction in an enantioselective way. A representative procedure for the enantioselective[4+2] cycloaddition reaction is as following: 1, 2-dichloroethane (1 mL) was added to the mixture of o-hydroxybenzyl alcohols (0.1 mmol), o-hydroxyl styrenes (0.12 mmol), the chiral phosphoric acid (0.005 mmol), and 3 Å molecular sieves (100 mg). After being stirred at 50 ℃ for 12 h, the reaction mixture was filtered to remove the molecular sieves, and the solid powder was washed with ethyl acetate. The resultant solution was concentrated under the reduced pressure to give the residue, which was purified through flash column chromatography on silica gel to afford the pure chiral chroman derivatives.
- o-hydroxybenzyl alcohol,
- o-hydroxyl styrene,
- [4+2] cycloaddition,
- chroman,
- asymmetric catalysis
1. [1]
  For some examples, see: (a) Ko, H.-H.; Jin, Y.-J.; Lu, T.-M.; Chen, I.-S. Chem. Biodiversity 2013, 10, 1269; (b) Kumar, S.; Deshpande, S.; Chandra, V.; Kitchlu, S.; Dwivedi, A.; Nayak, V. L.; Konwar, R.; Prabhakar; Yenamandra, S.; Sahu, D. P. Bioorg. Med. Chem. 2009, 17, 6832; (c) Hafez, H. N.; Hegab, M. I.; Ahmed-Farag, I. S.; El-Gazzar, A. B. A. Bioorg. Med. Chem. Lett. 2008, 18, 4538; (d) Poupelin, J. P.; Saint-Ruf, G.; Foussard-Blanpin, O.; Narcisse, G.; Uchida-Ernouf, G.; Lacroix, R. Eur. J. Med. Chem. 1978, 13, 67.
2. [2]
  Kumar, S.; Deshpande, S.; Chandra, V.; Kitchlu, S.; Dwivedi, A.; Nayak, V. L.; Konwar, R.; Prabhakar, Y. S.; Sahu, D. P. Bioorg. Med. Chem. 2009, 17, 6832; (b) Sangita; Dwivedi, A.; Prathipati, P.; Ray, S. Med. Chem. Res. 2010, 19, 915.
3. [3]
  For some examples, see: (a) Tripathi, S.; Dwivedy, I.; Dhar, J. D.; Dwivedy, A.; Ray, S. Bioorg. Med. Chem. Lett. 1997, 7, 2131; (b) Ferreira, S. B.; da Silva, F. de C.; Pinto, A. C.; Gonzaga, D. T. G.; Ferreira, V. F. J. Heterocycl. Chem. 2009, 46, 1080; (c) Zhang, H.; Zhu, L.; Wang, S.; Yao, Z.-J. J. Org. Chem. 2014, 79, 7063; (d) Yu, S.-Y.; Zhang, H.; Gao, Y.; Mo, L.; Wang, S.; Yao, Z.-J. J. Am. Chem. Soc. 2013, 135, 11402; (e) Enders, D.; Urbanietz, G.; Hahn, R.; Raabe, G. Synthesis 2012, 44, 773.
4. [4]
  For some reviews, see: (a) van de Water, R. W.; Pettus, T. R. R. Tetrahedron 2002, 58, 5367; (b) Pathak, T. P.; Sigman, M. S. J. Org. Chem. 2011, 76, 9210; (c) Willis, N. J.; Bray, C. D. Chem.-Eur. J. 2012, 18, 9160; (d) Wang, Z.; Sun, J. Synthesis 2015, 47, 3629; For some enantioselective examples, see: (e) Alden-Danforth, E.; Scerba, M. T.; Lectka, T. Org. Lett. 2008, 10, 4951; (f) Lv, H.; You, L.; Ye, S. Adv. Synth. Catal. 2009, 351, 2822; (g) Pathak, T. P.; Gligorich, K. M.; Welm, B. E.; Sigman, M. S. J. Am. Chem. Soc. 2010, 132, 7870; (h) Luan, Y.; Schaus, S. E. J. Am. Chem. Soc. 2012, 134, 19965; (i) Lv, H.; Jia, W. Q.; Sun, L. H.; Ye, S. Angew. Chem., Int. Ed. 2013, 52, 8607; (j) Izquierdo, J.; Orue, A.; Scheidt, K. A. J. Am. Chem. Soc. 2013, 135, 10634; (k) Wang, Z. B.; Ai, F. J.; Wang, Z.; Zhao, W. X.; Zhu, G. Y.; Lin, Z. Y.; Sun, J. W. J. Am. Chem. Soc. 2015, 137, 383.
5. [5]
  Wilcke, D.; Herdtweck, E.; Bach, T. Synlett 2011, 2011, 1235; (b) Zhao, W.; Wang, Z.; Chu, B.; Sun, J. Angew. Chem., Int. Ed. 2015, 54, 1910; (c) Saha, S.; Alamsetti, S. K.; Schneider, C. Chem. Commun. 2015, 51, 1461.
6. [6]
  El-Sepelgy, O.; Haseloff, S.; Alamsetti, S. K.; Schneider, C. Angew. Chem., Int. Ed. 2014, 53, 7923; (b) Hsiao, C. C.; Liao, H. H.; Rueping, M. Angew. Chem., Int. Ed. 2014, 53, 13258; (c) Saha, S.; Schneider, C. Chem. Eur. J. 2015, 21, 2348; (d) Saha, S.; Schneider, C. Org. Lett. 2015, 17, 648; (e) Zhao, J.-J.; Zhang, Y.-C.; Xu, M.-M.; Tang, M.; Shi, F. J. Org. Chem. 2015, 80, 10016.
7. [7]
  Zhao, J.-J.; Sun, S.-B.; He, S.-H.; Wu, Q.; Shi, F. Angew. Chem., Int. Ed. 2015, 54, 5460; (b) Hsiao, C.-C.; Raja, S.; Liao, H.-H.; Atodiresei, I.; Rueping, M. Angew. Chem., Int. Ed. 2015, 54, 5762.
8. [8]
  For early examples: (a) Akiyama, T.; Itoh, J.; Yokota, K.; Fuchibe, K. Angew. Chem., Int. Ed. 2004, 43, 1566; (b) Uraguchi, D.; Terada, M. J. Am. Chem. Soc. 2004, 126, 5356; For reviews: (c) Akiyama, T. Chem. Rev. 2007, 107, 5744; (d) Terada, M. Chem. Commun. 2008, 35, 4097; (e) Terada, M. Synthesis 2010, 1929; (f) Yu, J.; Shi, F.; Gong, L.-Z. Acc. Chem. Res. 2011, 44, 1156; (g) Parmar, D.; Sugiono, E.; Raja, S.; Rueping, M. Chem. Rev. 2014, 114, 9047; (h) Wu, X.; Li, M.-L.; Gong, L.-Z. Acta Chim. Sinica 2013, 71, 1091. (吴祥, 李明丽, 龚流柱, 化学学报, 2013, 71, 1091.); (i) Wu, H.; He, Y.-P.; Shi, F. Synthesis 2015, 47, 1990; For some selected examples, see: (j) Huang, J.-Z.; Luo, S.-W.; Gong, L.-Z. Acta Chim. Sinica 2013, 71, 879. (黄建洲, 罗时玮, 龚流柱, 化学学报, 2013, 71, 879); (k) Duan, D.; Yin, Q.; Wang, S.; Gu, Q.; You, S. Acta Chim. Sinica 2014, 72, 1001. (段德河, 殷勤, 王守国, 顾庆, 游书力, 化学学报, 2014, 72, 1001.); (l) Shi, L.; Ji, Y.; Huang, W.; Zhou, Y. Acta Chim. Sinica 2014, 72, 820. (时磊, 姬悦, 黄文学, 周永贵, 化学学报, 2014, 72, 820.); (m) Lv, J.; Qin, Y.; Cheng, J.; Luo, S. Acta Chim. Sinica 2014, 72, 809. (吕健, 秦岩, 程津培, 罗三中, 化学学报, 2014, 72, 809.); (n) Wang, S.-G.; You, S.-L. Angew. Chem., Int. Ed. 2014, 53, 2194; (o) Wang, S.-G.; Yin, Q.; Zhuo, C.-X.; You, S.-L. Angew. Chem., Int. Ed. 2015, 54, 647.
9. [9]
  Chen, X.-H.; Zhang, W.-Q.; Gong, L.-Z. J. Am. Chem. Soc. 2008, 130, 5652; (b) He, L.; Chen, X.-H.; Wang, D.-N.; Luo, S.-W.; Zhang, W.-Q.; Yu, J.; Ren, L.; Gong, L.-Z. J. Am. Chem. Soc. 2011, 133, 13504.
1. [1]
  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
2. [2]
  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
3. [3]
  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
4. [4]
  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
5. [5]
  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
6. [6]
  Lihui Jiang , Wanrong Dong , Hua Yang , Yongqing Xia , Hongjian Peng , Jun Yuan , Xiaoqian Hu , Zihan Zeng , Yingping Zou , Yiming Luo . Study on Extraction of p-Hydroxyacetophenone. University Chemistry, 2024, 39(11): 259-268. doi: 10.12461/PKU.DXHX202402056
7. [7]
  Hailian Tang , Siyuan Chen , Qiaoyun Liu , Guoyi Bai , Botao Qiao , Fei Liu . Stabilized Rh/hydroxyapatite Catalyst for Furfuryl Alcohol Hydrogenation: Application of Oxidative Strong Metal-Support Interactions in Reducing Conditions. Acta Physico-Chimica Sinica, 2025, 41(4): 100036-. doi: 10.3866/PKU.WHXB202408004
8. [8]
  Ruolin CHENG , Haoran WANG , Jing REN , Yingying MA , Huagen LIANG . Efficient photocatalytic CO₂ cycloaddition over W₁₈O₄₉/NH₂-UiO-66 composite catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 523-532. doi: 10.11862/CJIC.20230349
9. [9]
  Chengqian Mao , Yanghan Chen , Haotong Bai , Junru Huang , Junpeng Zhuang . Photodimerization of Styrylpyridinium Salt and Its Application in Silk Screen Printing. University Chemistry, 2024, 39(5): 354-362. doi: 10.3866/PKU.DXHX202312014
10. [10]
  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
11. [11]
  Tao Cao , Fang Fang , Nianguang Li , Yinan Zhang , Qichen Zhan . Green Synthesis of p-Hydroxybenzonitrile Catalyzed by Spinach Extracts under Red-Light Irradiation: Research and Exploration of Innovative Experiments for Pharmacy Undergraduates. University Chemistry, 2024, 39(5): 63-69. doi: 10.3866/PKU.DXHX202309098
12. [12]
  Zhanggui DUAN , Yi PEI , Shanshan ZHENG , Zhaoyang WANG , Yongguang WANG , Junjie WANG , Yang HU , Chunxin LÜ , Wei ZHONG . Preparation of UiO-66-NH₂ supported copper catalyst and its catalytic activity on alcohol oxidation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 496-506. doi: 10.11862/CJIC.20230317
13. [13]
  Yifeng TAN , Ping CAO , Kai MA , Jingtong LI , Yuheng WANG . Synthesis of pentaerythritol tetra(2-ethylthylhexoate) catalyzed by h-MoO₃/SiO₂. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2155-2162. doi: 10.11862/CJIC.20240147
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]
  Yanglin Jiang , Mingqing Chen , Min Liang , Yige Yao , Yan Zhang , Peng Wang , Jianping Zhang . Experimental and Theoretical Investigations of Solvent Polarity Effect on ESIPT Mechanism in 4′-N,N-diethylamino-3-hydroxybenzoflavone. Acta Physico-Chimica Sinica, 2025, 41(2): 100012-. doi: 10.3866/PKU.WHXB202309027
16. [16]
  Zhanhui Yang , Jiaxi Xu . (m+n+…) or [m+n+…]cycloaddition?. University Chemistry, 2025, 40(3): 387-389. doi: 10.12461/PKU.DXHX202406032
17. [17]
  Jingke LIU , Jia CHEN , Yingchao HAN . Nano hydroxyapatite stable suspension system: Preparation and cobalt adsorption performance. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1763-1774. doi: 10.11862/CJIC.20240060
18. [18]
  Jiahui YU , Jixian DONG , Yutong ZHAO , Fuping ZHAO , Bo GE , Xipeng PU , Dafeng ZHANG . The morphology control and full-spectrum photodegradation tetracycline performance of microwave-hydrothermal synthesized BiVO₄:Yb³⁺,Er³⁺ photocatalyst. Journal of Fuel Chemistry and Technology, 2025, 53(3): 348-359. doi: 10.1016/S1872-5813(24)60514-1
19. [19]
  Aili Feng , Xin Lu , Peng Liu , Dongju Zhang . Computational Chemistry Study of Acid-Catalyzed Esterification Reactions between Carboxylic Acids and Alcohols. University Chemistry, 2025, 40(3): 92-99. doi: 10.12461/PKU.DXHX202405072
20. [20]
  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

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(702)
HTML views(129)

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