Citation: TANG Pingsheng, WANG Bo. 1, 6-Addition of Terminal Alkynes to p-Quinone Methides[J]. Chinese Journal of Applied Chemistry, ;2017, 34(6): 664-670. doi: 10.11944/j.issn.1000-0518.2017.06.160379 shu

1, 6-Addition of Terminal Alkynes to p-Quinone Methides

TANG Pingsheng ^a,b ,
WANG Bo ^a,#,,

a.
Green Chemistry and Process Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, China
b.
University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: WANG Bo, wangbo@ciac.ac.cn
Received Date: 21 September 2016
Revised Date: 8 October 2016
Accepted Date: 9 October 2016

Fund Project: Jilin Scientific and Technological Development Program 20130727051YYJilin Scientific and Technological Development Program 20150414043GH

Figures(4)

In order to synthesize selaginellin family natural products, a methodology of 1, 6-addition of alkynyl lithium to p-quinone methides was developed. The reaction conditions and scope and limitations of substrates of this reaction were investigated. The results show that the electronic effect of substituents on the phenyl ring of p-quinone methides exhibits significant effects on reaction rates and yields. Electro-withdrawing groups accelerate the addition and lead to good yields. On the other hand, electro-donating groups deactivate p-quinone methides, and low yield is observed presumably due to the equilibrium nature of the reaction. Besides, all alkynes surveyed provide corresponding products in high yield. This novel method can provide a rapid assembly of the skeleton of selaginellin natural products.
- p-quinone methide,
- terminal alkyne,
- 1, 6-addition
1. [1]
  Turner A B. Quinone Methides[J]. Q Rev, Chem Soc, 1964,18(4):347-360. doi: 10.1039/qr9641800347
2. [2]
  Chu W D, Zhang L F, Bao X. Asymmetric Catalytic 1, 6-Conjugate Addition/Aromatization of para-Quinone Methides:Enantioselective Introduction of Functionalized Diarylmethine Stereogenic Centers[J]. Angew Chem Int Ed, 2013,52(35):9229-9233. doi: 10.1002/anie.201303928
3. [3]
  Caruana L, Kniep F, Johansen T K. A New Organocatalytic Concept for Asymmetric α-Alkylation of Aldehydes[J]. J Am Chem Soc, 2014,136(45):15929-15932. doi: 10.1021/ja510475n
4. [4]
  Wang Z, Wong Y F, Sun J. Catalytic Asymmetric 1, 6-Conjugate Addition of para-Quinone Methides:Formation of All-Carbon Quaternary Stereocenters[J]. Angew Chem Int Ed, 2015,54(46):13711-13714. doi: 10.1002/anie.201506701
5. [5]
  Lou Y, Cao P, Jia T. Copper-Catalyzed Enantioselective 1, 6-Boration of para-Quinone Methides and Efficient Transformation of gem-Diarylmethine Boronates to Triarylmethanes[J]. Angew Chem Int Ed, 2015,54(41):12134-12138. doi: 10.1002/anie.201505926
6. [6]
  Dong N, Zhang Z P, Xue X S. Phosphoric Acid Catalyzed Asymmetric 1, 6-Conjugate Addition of Thioacetic Acid to para-Quinone Methides[J]. Angew Chem Int Ed, 2016,55(4):1460-1464. doi: 10.1002/anie.201509110
7. [7]
  Lopez A, Parra A, Jarava-Barrera C. Copper-catalyzed Silylation of p-Quinone Methides:New Entry to Dibenzylic Silanes[J]. Chem Commun, 2015,51(100):17684-17687. doi: 10.1039/C5CC06653K
8. [8]
  Jarava-Barrera C, Parra A, López A. Copper-Catalyzed Borylative Aromatization of p-Quinone Methides:Enantioselective Synthesis of Dibenzylic Boronates[J]. ACS Catal, 2016,6(1):442-446. doi: 10.1021/acscatal.5b02742
9. [9]
  Hatchard W R. Syntheses by Free-radical Reactions.Ⅶ.The Reaction of 2, 6-Di-t-butyl-4-methylphenol and 2, 6-Di-t-butyl-4-isopropylphenol with Chloroprene[J]. J Am Chem Soc, 1958,80(14):3640-3642. doi: 10.1021/ja01547a042
10. [10]
  McClure J D. Synthesis of Spiroundecatrienones from 2, 6-Di-t-butylquinone Methide and Butadienes[J]. J Org Chem, 1962,27(7):2365-2368. doi: 10.1021/jo01054a018
11. [11]
  Roper J M, Everly C R. Direct Synthesis of Spiro[5.5] undeca-1, 4, 7-trienones from Phenols via a Quinone Methide Intermediate[J]. J Org Chem, 1988,53(11):2639-2642. doi: 10.1021/jo00246a050
12. [12]
  Angle S R, Arnaiz D. Formal[3+2] Cycloaddition of Benzylic Cations with Alkenes[J]. J Org Chem, 1992,57(22):5937-5947. doi: 10.1021/jo00048a029
13. [13]
  Kim S, Kitano Y, Tada M. Alkylindan Synthesis via an Intermolecular[3+2] Cycloaddition Between Unactivated Alkenes and in situ Generated p-Quinomethanes[J]. Tetrahedron Lett, 2000,41(36):7079-7083. doi: 10.1016/S0040-4039(00)01216-8
14. [14]
  Zhang L P, Liang Y M, Wei X C. A New Unusual Natural Pigment from Selaginella sinensis and Its Noticeable Physicochemical Properties[J]. J Org Chem, 2007,72(10):3921-3924. doi: 10.1021/jo0701177
15. [15]
  Cheng X L, Ma S C, Yu J D. Selaginellin A and B, Two Novel Natural Pigments Isolated from Selaginella tamariscina[J]. Chem Pharm Bull, 2008,56(7):982-984. doi: 10.1248/cpb.56.982
16. [16]
  TAN Guishan. Studies on Chemical Constituent from Selaginella Pulvinata Maxim and Effect of Selaginellin on Senescence of Endothelial Cells[D]. Changsha:Central South University, 2007(in Chinese).
17. [17]
  ZENG Qinghai, TU Chao, FAN Fan. Research Progress of Selaginellin and the Antitumor Activity of Selaginella[J]. Anti-tumor Pharm, 2012,2(6):402-406.
18. [18]
  Zanarotti A. Synthesis and Reactivity of Vinyl Quinone Methides[J]. J Org Chem, 1985,50(7):941-945. doi: 10.1021/jo00207a006
1. [1]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
2. [2]
  Yujie WANG , Laobang WANG , Zheng ZHANG , Qi LIU , Jianping LANG . Construction of W/Cu/S cluster-based supramolecular compounds via alkynyl/sulfur cycloaddition and their third-order nonlinear optical properties. Chinese Journal of Inorganic Chemistry, 2025, 41(10): 2069-2077. doi: 10.11862/CJIC.20250129
3. [3]
  Xiaofeng Xia , Jielian Zhu . Innovative Comprehensive Experimental Design: Synthesis of 6-Fluoro-N-benzoyl Tetrahydroquinoline. University Chemistry, 2024, 39(10): 344-352. doi: 10.12461/PKU.DXHX202405063
4. [4]
  Aiyi Xin , Jiawei Li , Xinyang Ran , Chuanjiang Fu , Zhiguo Wang . Collaborative Science and Education Based Experimental Design in Organic Chemistry: A Case Study of the Nucleophilic Substitution Reaction of 2-Hydroxymethyl-4,6-Di-Tert-Butylphenol. University Chemistry, 2025, 40(5): 366-375. doi: 10.12461/PKU.DXHX202407031
5. [5]
  Xiaoning TANG , Junnan LIU , Xingfu YANG , Jie LEI , Qiuyang LUO , Shu XIA , An XUE . Effect of sodium alginate-sodium carboxymethylcellulose gel layer on the stability of Zn anodes. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1452-1460. doi: 10.11862/CJIC.20240191
6. [6]
  Mengyang LI , Hao XU , Zhonghao NIU , Chunhua GONG , Weihui ZHONG , Jingli XIE . Highly effective catalytic synthesis of β-amino alcohols by using viologen-polyoxometalate hybrid materials. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1294-1300. doi: 10.11862/CJIC.20250080
7. [7]
  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
8. [8]
  Chao WU , Qingxiu SHI , Tao XU , Zhengxi PENG , Zhongping XIONG , Yinglin ZHANG , Yujun SI , Chaozhong GUO . Enhancement of oxygen reduction reaction performance of iron-nitrogen doped carbon based catalysts by sodium carboxymethyl cellulose pre-deoxygenation. Chinese Journal of Inorganic Chemistry, 2026, 42(4): 737-746. doi: 10.11862/CJIC.20250305
9. [9]
  Xiaoyang Li , Xiaowei Huang , Yimeng Zhang , Huan Liu , Shao Jin , Junpeng Zhuang . Comprehensive Chemical Experiments on the Synthesis of 1,3-Dibromo-5,5-Dimethylhydantoin and Its Application as a Brominating Reagent. University Chemistry, 2025, 40(7): 286-293. doi: 10.12461/PKU.DXHX202408035
10. [10]
  Zhengyu Zhou , Huiqin Yao , Youlin Wu , Teng Li , Noritatsu Tsubaki , Zhiliang Jin . Synergistic Effect of Cu-Graphdiyne/Transition Bimetallic Tungstate Formed S-Scheme Heterojunction for Enhanced Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2024, 40(10): 2312010-0. doi: 10.3866/PKU.WHXB202312010
11. [11]
  Yihui Song , Shangshang Qin , Kai Wu , Chengyun Jin , Bin Yu . 生物化学在高水平创新型药学人才培养中的交叉融合应用——以去甲基化酶LSD1抑制剂的活性评价为例. University Chemistry, 2025, 40(6): 341-352. doi: 10.12461/PKU.DXHX202406018
12. [12]
  Qilin YU , Yifei XU , Pengjun ZHANG , Shuwei HAO , Chongqiang ZHU , Chunhui YANG . Effect of regulating K⁺/Na⁺ ratio on the structure and optical properties of double perovskite Cs₂NaBiCl₆: Mn²⁺. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1058-1067. doi: 10.11862/CJIC.20240418
13. [13]
  Hexing SONG , Zan SUN . Synthesis, crystal structure, Hirshfeld surface analysis, and fluorescent sensing for Fe³⁺ of an Mn(Ⅱ) complex based on 1-naphthalic acid. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 885-892. doi: 10.11862/CJIC.20240402
14. [14]
  Yuanqing Wang , Yusong Pan , Hongwu Zhu , Yanlei Xiang , Rong Han , Run Huang , Chao Du , Chengling Pan . Enhanced Catalytic Activity of Bi₂WO₆ for Organic Pollutants Degradation under the Synergism between Advanced Oxidative Processes and Visible Light Irradiation. Acta Physico-Chimica Sinica, 2024, 40(4): 2304050-0. doi: 10.3866/PKU.WHXB202304050
15. [15]
  Zhanhui Yang , Jiaxi Xu . (m+n+…) or [m+n+…]cycloaddition?. University Chemistry, 2025, 40(3): 387-389. doi: 10.12461/PKU.DXHX202406032
16. [16]
  Chi Li , Jichao Wan , Qiyu Long , Hui Lv , Ying Xiong . N-Heterocyclic Carbene (NHC)-Catalyzed Amidation of Aldehydes with Nitroso Compounds. University Chemistry, 2024, 39(5): 388-395. doi: 10.3866/PKU.DXHX202312016
17. [17]
  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
18. [18]
  Xinhao Yan , Guoliang Hu , Ruixi Chen , Hongyu Liu , Qizhi Yao , Jiao Li , Lingling Li . Polyethylene Glycol-Ammonium Sulfate-Nitroso R Salt System for the Separation of Cobalt (II). University Chemistry, 2024, 39(6): 287-294. doi: 10.3866/PKU.DXHX202310073
19. [19]
  Xiaohui Zhang , Xingchen He , Yuanyi Zhou , Pengyu Liu , Yuxiang Qin , Yanqin Xu , Yan Xiong . Improvement of Methyl Orange Preparation Experiment Using Digital-Intelligent Device System. University Chemistry, 2026, 41(1): 159-168. doi: 10.12461/PKU.DXHX202506018
20. [20]
  Jiajia Li , Xiangyu Zhang , Zhihan Yuan , Zhengyang Qian , Jian Zhu . 3D Printing Based on Photo-Induced Reversible Addition-Fragmentation Chain Transfer Polymerization. University Chemistry, 2024, 39(5): 11-19. doi: 10.3866/PKU.DXHX202309073

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(912)
HTML views(177)

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