Citation: Li Kunyu, Bai Lu, Luan Xinjun. Pd-Catalyzed Dearomative Spirocyclization of Bromophenols via[2+2+1] Strategy[J]. Chinese Journal of Organic Chemistry, ;2019, 39(8): 2211-2217. doi: 10.6023/cjoc201903065 shu

Pd-Catalyzed Dearomative Spirocyclization of Bromophenols via[2+2+1] Strategy

Li Kunyu ^† ,
Bai Lu ^†,, ,
Luan Xinjun ^,

College of Chemistry & Materials Science, Northwest University, Xi'an 710127

Corresponding author: Bai Lu, xluan@nwu.edu.cn Luan Xinjun, xluan@nwu.edu.cn

^†

Received Date: 28 March 2019
Revised Date: 26 April 2019
Available Online: 28 August 2019
Fund Project: the National Natural Science Foundation of China 21672169the Key Laboratory Project of Xi'an City 201805058ZD9CG42Project supported by the National Natural Science Foundation of China (No. 21672169), and the Key Laboratory Project of Xi'an City (No. 201805058ZD9CG42)

Figures(1)

A novel palladium(0)-catalyzed dearomative spirocyclization reaction of bromophenols has been developed for building a series of spirocyclic architectures containing a quaternary carbon center via[2+2+1] strategy. This method employs inexpensive bromophenols and easily accessible alkynes. It exhibits a broad substrate scope in good yields. Notably, this transformation can be realized with high regioselectivity (>19:1 rr) when using unsymmetrical alkynes, which greatly expands the research scope of phenol dearomatization.
- transition-metal-catalyzed,
- dearomatization,
- spirocyclization,
- bromophenols
1. [1]
  (a) Edrada, R. A.; Stessman, C. C.; Crews, P. J. Nat. Prod. 2003, 66, 939.
  (b) Cheng, P.; Ma, Y.; Yao, S.; Zhang, Q.; Wang, E.; Yan, M.; Zhang, X.; Zhang, F.; Chen, J. Bioorg. Med. Chem. Lett. 2007, 17, 5316.
  (c) Zhang, Y.; Ge, H.; Zhao, W.; Dong, H.; Xu, Q.; Li, S.; Li, J.; Zhang, J.; Song, Y.; Tan, R. Angew. Chem., Int. Ed. 2008, 47, 5823.
  (d) Fu, J.; Qin, J.; Zeng, Q.; Huang, Y.; Jin, H.; Zhang, W. Chem. Pharm. Bull. 2010, 58, 1263.
  (e) Zhao, J. H.; Wang, Z. Q.; Zhou, Y.; Zhu, G. N.; Yu, C. M. Chin. J. Org. Chem. 2011, 31, 3031(in Chinese).
  (赵金浩, 王宗成, 周勇, 朱国念, 俞传明, 有机化学, 2011, 31, 3031.)
  (f) Park, H. B.; Kim, Y.-J.; Lee, J. K.; Lee, K. R.; Kwon, H. C. Org. Lett. 2012, 14, 5002.
  (g) Du, W.; Hung, H.; Kuo, P.; Hwang, T.; Shiu, L.; Shiu, K.; Lee, E.; Tai, S.; Wu, T. Org. Lett. 2016, 18, 3042.
  (h) Ma, Y.; Fan, C.; Chin. J. Org. Chem. 2016, 36, 2380(in Chinese).
  (马养民, 范超, 有机化学, 2016, 36, 2380.)
2. [2]
  Reviews: (a) Roche, S. P.; Porco, Jr., J. Angew. Chem., Int. Ed. 2011, 50, 4068.
  (b) Zhuo, C.; Zhang, W.; You, S. Angew. Chem., Int. Ed. 2012, 51, 12662.
  (c) Wu, W.-T.; Zhang, L.; You, S.-L. Chem. Soc. Rev. 2016, 45, 1570.
  (d) James, M. J.; O'Brien, P.; Taylor, R. J. K.; Unsworth, W. P. Chem. Eur. J. 2016, 22, 2856.
  (e) Nemoto, T.; Hamada, Y. Synlett 2016, 2301.
  (f) Wang, H.; Luan, X. Org. Biomol. Chem. 2016, 14, 9451.
  (g) Liang, X.-W.; Chen, X.; Zhang, Z.; You S.-L. Chin. Chem. Lett. 2018, 29, 1212.
  (h) Wang, K.-K.; Du, W.; Zhu, J.; Chen Y.-C. Chin. Chem. Lett. 2017, 28, 512.
  (i) Wu, W.-T.; Zhang, L. M.; You, S.-L. Acta Chim. Sinica 2017, 75, 419(in Chinese).
  (吴文挺, 张立明, 游书力, 化学学报, 2017, 75, 419.)
3. [3]
  (a) Tyman, J. H. P. Synthetic and Natural Phenol; Elsevier: New York, 1996.
  (b) Rappoport, Z. The Chemistry of Phenols; John Wiley & Sons Ltd.: Chichester, 2003.
  (c) Weber, M.; Weber, M.; KleineBoymann, M. Phenol. In Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2004.
4. [4]
  For selected reviews, see: (a) Kündig, E. P.; Rape, A. Top. Organomet. Chem. 2004, 7, 95.
  (b) Quideau, S.; Pouységu, L.; Deffieus, D. Synlett 2008, 467.
  (c) Roche, S. P.; Porco, J. A., Jr. Angew. Chem., Int. Ed. 2011, 50, 4068.
  (d) Zhuo, C. X.; Zhang, W.; You, S. L. Angew. Chem., Int. Ed. 2012, 51, 12662.
  (e) Lü, W. W.; He, X. C.; Shi, M.; Wang, F. J. Chin. J. Org. Chem. 2019, 39, 532(in Chinese).
  (吕雯雯, 贺信淳, 施敏, 王飞军, 有机化学, 2019, 39, 532.)
  (f) Cui, N.; Zhao, Y.; Wang, Y. X. Chin. J. Org. Chem. 2017, 37, 20(in Chinese). (崔娜, 赵宇, 王云侠, 有机化学, 2017, 37, 20.)
  (g) Lin, S. B.; He, X. R.; Meng, J. P.; Gu, H. N.; Zhang, P. Z.; Wu, J. Chin. J. Org. Chem. 2017, 37, 1864(in Chinese).
  (蔺松波, 何兴瑞, 孟金鹏, 顾海宁, 张培志, 吴军, 有机化学, 2017, 37, 1864.)
5. [5]
  (a) Roche, S. P.; Porco, J., Jr Angew. Chem., Int. Ed. 2011, 50, 4068.
  (b) Zhuo, C.; Zhang, W.; You, S. Angew. Chem., Int. Ed. 2012, 51, 12662.
  (c) Zhuo, C.; Zheng, C.; You, S. Acc. Chem. Res. 2014, 47, 2558.
  (d) Zheng, C.; You, S. Chem. 2016, 1, 830.
  (e) Wu, W.; Zhang, L.; You, S. Chem. Soc. Rev. 2016, 45, 1570.
  (f) Nemoto, T.; Hamada, Y. Synlett 2016, 27, 2301.
  (g) Wang, H.; Luan, X. Org. Biomol. Chem. 2016, 14, 9451.
6. [6]
  Nemoto, T.; Ishige, Y.; Yoshida, M.; Kohno, Y.; Kanematsu, M.; Hamada, Y. Org. Lett. 2010, 12, 5020. doi: 10.1021/ol102190s
7. [7]
  Rousseaux, S.; García-Fortanet, J.; Del Aguila Sanchez, M. A.; Buchwald, S. L. J. Am. Chem. Soc. 2011, 133, 9282. doi: 10.1021/ja203644q
8. [8]
  Wu, Q.; Liu, W.; Zhuo, C.; Rong, Z.; Ye, K.; You, S. Angew. Chem., Int. Ed. 2011, 50, 4455. doi: 10.1002/anie.201100206
9. [9]
  (a) Nan, J.; Zuo, Z.; Luo, L.; Bai, L.; Zheng, H.; Yuan, Y.; Liu, J.; Luan, X.; Wang, Y. J. Am. Chem. Soc. 2013, 135, 17306.
  (b) Zuo, Z.; Yang, X.; Liu, J.; Nan, J.; Bai, L.; Wang, Y.; Luan, X. J. Org. Chem. 2015, 80, 3349.
10. [10]
  Seoane, A.; Casanova, N.; Quiñones, N.; Mascareñas, J. L.; Gulías, M. J. Am. Chem. Soc. 2014, 136, 7607. doi: 10.1021/ja5034952
11. [11]
  Kujawa, S.; Best, D.; Burns, D. J.; Lam, H. W. Chem. Eur. J. 2014, 20, 8599. doi: 10.1002/chem.201403454
12. [12]
  (a) Zheng, J.; Wang, S.; Zheng, C.; You, S. J. Am. Chem. Soc. 2015, 137, 4880.
  (b) Zheng, C.; Zheng, J.; You, S. ACS Catal. 2016, 6, 262.
13. [13]
  Gu, S.; Luo, L.; Liu, J.; Bai, L.; Zheng, H.; Wang, Y.; Luan, X. Org. Lett. 2014, 16, 6132. doi: 10.1021/ol502997d
14. [14]
  Bai, L.; Yuan, Y.; Liu, J.; Wu, J.; Han, L.; Wang, H.; Wang, Y.; Luan, X. Angew. Chem., Int. Ed. 2016, 55, 6946. doi: 10.1002/anie.201601570
1. [1]
  Geyang Song , Dong Xue , Gang Li . Recent Advances in Transition Metal-Catalyzed Synthesis of Anilines from Aryl Halides. University Chemistry, 2024, 39(2): 321-329. doi: 10.3866/PKU.DXHX202308030
2. [2]
  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
3. [3]
  Caixia Lin , Ting Liu , Zhaojiang Shi , Hong Yan , Keyin Ye , Yaofeng Yuan . Innovative Experiment of Electrochemical Dearomative Spirocyclization of N-Acyl Sulfonamides. University Chemistry, 2025, 40(4): 359-366. doi: 10.12461/PKU.DXHX202406107
4. [4]
  Jinyao Du , Xingchao Zang , Ningning Xu , Yongjun Liu , Weisi Guo . Electrochemical Thiocyanation of 4-Bromoethylbenzene. University Chemistry, 2024, 39(6): 312-317. doi: 10.3866/PKU.DXHX202310039
5. [5]
  Zhongyan Cao , Shengnan Jin , Yuxia Wang , Yiyi Chen , Xianqiang Kong , Yuanqing Xu . Advances in Highly Selective Reactions Involving Phenol Derivatives as Aryl Radical Precursors. University Chemistry, 2025, 40(4): 245-252. doi: 10.12461/PKU.DXHX202405186
6. [6]
  Fei Xie , Chengcheng Yuan , Haiyan Tan , Alireza Z. Moshfegh , Bicheng Zhu , Jiaguo Yu . d带中心调控过渡金属单原子负载COF吸附O₂的理论计算研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2407013-. doi: 10.3866/PKU.WHXB202407013
7. [7]
  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
8. [8]
  Lina Guo , Ruizhe Li , Chuang Sun , Xiaoli Luo , Yiqiu Shi , Hong Yuan , Shuxin Ouyang , Tierui Zhang . 层状双金属氢氧化物的层间阴离子对衍生的Ni-Al₂O₃催化剂光热催化CO₂甲烷化反应的影响. Acta Physico-Chimica Sinica, 2025, 41(1): 2309002-. doi: 10.3866/PKU.WHXB202309002
9. [9]
  Shihui Shi , Haoyu Li , Shaojie Han , Yifan Yao , Siqi Liu . Regioselectively Synthesis of Halogenated Arenes via Self-Assembly and Synergistic Catalysis Strategy. University Chemistry, 2024, 39(5): 336-344. doi: 10.3866/PKU.DXHX202312002
10. [10]
  Hongting Yan , Aili Feng , Rongxiu Zhu , Lei Liu , Dongju Zhang . Reexamination of the Iodine-Catalyzed Chlorination Reaction of Chlorobenzene Using Computational Chemistry Methods. University Chemistry, 2025, 40(3): 16-22. doi: 10.12461/PKU.DXHX202403010
11. [11]
  Lu XU , Chengyu ZHANG , Wenjuan JI , Haiying YANG , Yunlong FU . Zinc metal-organic framework with high-density free carboxyl oxygen functionalized pore walls for targeted electrochemical sensing of paracetamol. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 907-918. doi: 10.11862/CJIC.20230431
12. [12]
  Xiaoling LUO , Pintian ZOU , Xiaoyan WANG , Zheng LIU , Xiangfei KONG , Qun TANG , Sheng WANG . Synthesis, crystal structures, and properties of lanthanide metal-organic frameworks based on 2, 5-dibromoterephthalic acid ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1143-1150. doi: 10.11862/CJIC.20230271
13. [13]
  Xiaofeng Zhu , Bingbing Xiao , Jiaxin Su , Shuai Wang , Qingran Zhang , Jun Wang . Transition Metal Oxides/Chalcogenides for Electrochemical Oxygen Reduction into Hydrogen Peroxides. Acta Physico-Chimica Sinica, 2024, 40(12): 2407005-. doi: 10.3866/PKU.WHXB202407005
14. [14]
  Hongyi Zhang , Zhihong Shi , Zhijun Zhang . A New Strategy for “De-formulized” Calculation of Dynamic Buffer Capacity in Analytical Chemistry Education. University Chemistry, 2024, 39(3): 390-394. doi: 10.3866/PKU.DXHX202309030
15. [15]
  Shengbiao Zheng , Liang Li , Nini Zhang , Ruimin Bao , Ruizhang Hu , Jing Tang . Metal-Organic Framework-Derived Materials Modified Electrode for Electrochemical Sensing of Tert-Butylhydroquinone: A Recommended Comprehensive Chemistry Experiment for Translating Research Results. University Chemistry, 2024, 39(7): 345-353. doi: 10.3866/PKU.DXHX202310096
16. [16]
  Xinghai Liu , Hongke Wu . Exploration and Practice of Ideological and Political Education in Heterocyclic Chemistry Based on "Fentanyl" Event. University Chemistry, 2024, 39(8): 359-364. doi: 10.3866/PKU.DXHX202312100
17. [17]
  Guimin ZHANG , Wenjuan MA , Wenqiang DING , Zhengyi FU . Synthesis and catalytic properties of hollow AgPd bimetallic nanospheres. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 963-971. doi: 10.11862/CJIC.20230293
18. [18]
  Wenxiu Yang , Jinfeng Zhang , Quanlong Xu , Yun Yang , Lijie Zhang . Bimetallic AuCu Alloy Decorated Covalent Organic Frameworks for Efficient Photocatalytic Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312014-. doi: 10.3866/PKU.WHXB202312014
19. [19]
  Ping ZHANG , Chenchen ZHAO , Xiaoyun CUI , Bing XIE , Yihan LIU , Haiyu LIN , Jiale ZHANG , Yu'nan CHEN . Preparation and adsorption-photocatalytic performance of ZnAl@layered double oxides. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1965-1974. doi: 10.11862/CJIC.20240014
20. [20]
  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

Get Citation

PDF

XML

Metrics

PDF Downloads(7)
Abstract views(906)
HTML views(156)

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