Citation: Wang Kai-Kai, Du Wei, Zhu Jin, Chen Ying-Chun. Construction of polycyclic spirooxindoles through[3+2] annulations of Morita-Baylis-Hillman carbonates and 3-nitro-7-azaindoles[J]. Chinese Chemical Letters, ;2017, 28(3): 512-516. doi: 10.1016/j.cclet.2016.11.003 shu

Construction of polycyclic spirooxindoles through[3+2] annulations of Morita-Baylis-Hillman carbonates and 3-nitro-7-azaindoles

Wang Kai-Kai ^a,c ,
Du Wei ^b ,
Zhu Jin ^a ,
Chen Ying-Chun ^b,,

a.
Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, China
b.
Key Laboratory of Drug-Targeting and Drug Delivery System of the Ministry of Education, West China School of Pharmacy, Sichuan University, Chengdu 610041, China
c.
University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: Chen Ying-Chun, ycchen@scu.edu.cn
Received Date: 6 September 2016
Revised Date: 20 October 2016
Accepted Date: 20 October 2016
Available Online: 9 March 2016

Figures(4)

A mild and efficient dearomatic[3+2] annulation reaction of 3-nitro-7-azaindoles and Morita Baylis Hillman carbonates from isatins was developed catalyzed by DMAP, affording the corresponding polycyclic spirooxindoles containing fused azaindoline architectures andvicinal quaternarycenters in excellent yields (up to 96%) with high regio-and diastereoselectivity (dr>19:1). Moderate enantioselectivity (79% ee) was obtained by employing a chiral DMAP-type Lewis base catalyst.
- Morita-Baylis-Hillman carbonates,
- [3+2] annulation,
- Spirooxindoles,
- Regioselectivity,
- Dearomatization
1. [1]
  (a) P.M. Barbour, L.J. Marholz, L. Chang, W.Q. Xu, X. Wang, Gold approaches to polycyclic indole alkaloids, Chem. Lett. 43(2014) 572-578;
  (b) K. Walton, J. Berry, Indole alkaloids of the stigonematales (cyanophyta):chemical diversity, biosynthesis and biological activity, Mar. Drugs 14(2016) 73-100;
  (c) W. Zi, Z. Zuo, D. Ma, Intramolecular dearomative oxidative coupling of indoles:a unified strategy for the total synthesis of indoline alkaloids, Acc. Chem. Res. 48(2015) 702-711;
  (d) A. Steven, L.E. Overman, Total synthesis of complex cyclotryptamine alkaloids:stereocontrolled construction of quaternary carbon stereocenters, Angew. Chem. Int. Ed. 46(2007) 5488-5508.
2. [2]
  (a) Y.N. Gao, Q. Xu, M. Shi, Enantioselective synthesis of polycyclic indole derivatives based on aza-Morita-Baylis-Hillman reaction, ACS Catal. 5(2015) 6608-6614;
  (b) J.X. Liu, M. Shen, Y.D. Zhang, et al., A new entry to polycyclic indole skeletons via palladium-catalyzed intramolecular heteroannulation, Org. Lett. 8(2006) 3573-3575;
  (c) T. Wang, S. Shi, D. Pflasterer, et al., Synthesis of polycyclic indole skeletons by a gold (Ⅰ)-catalyzed cascade reaction, Chem. Eur. J. 20(2014) 292-296;
  (d) S.P. Wong, K.W. Chong, K.H. Lim, et al., Arborisidine and Arbornamine, two monoterpenoid indole alkaloids with new polycyclic carbon-nitrogen skeletons derived from a common pericine precursor, Org. Lett. 18(2016) 1618-1621;
  (e) J.M. Yang, P.H. Li, Y. Wei, X.Y. Tang, M. Shi, Gold (Ⅰ)-catalyzed highly stereoselective synthesis of polycyclic indolines:the construction of four contiguous stereocenters, Chem. Commun. 52(2016) 346-349.
3. [3]
  (a) G. Bartoli, G. Bencivenni, R. Dalpozzo, Organocatalytic strategies for the asymmetric functionalization of indoles, Chem. Soc. Rev. 39(2010) 4449-4465;
  (b) T.B. Poulsen, K.A. Jørgensen, Catalytic asymmetric Friedel-Crafts alkylation reactions-copper showed the way, Chem. Rev. 108(2008) 2903-2915;
  (c) S.-L. You, Q. Cai, M. Zeng, Chiral Bronsted acid catalyzed Friedel-Crafts alkylation reactions, Chem. Soc. Rev. 38(2009) 2190-2201;
  (d) M. Bandini, A. Eichholzer, Catalytic functionalization of indoles in a new dimension, Angew. Chem. Int. Ed. 48(2009) 9608-9644;
  (e) C.C.J. Loh, D. Enders, Exploiting the electrophilic properties of indole intermediates:new options in designing asymmetric reactions, Angew. Chem. Int. Ed. 51(2012) 46-48.
4. [4]
  (a) M. Bandini, Electrophilicity:the "dark-side" of indole chemistry, Org. Biomol. Chem. 11(2013) 5206-5212;
  (b) G.W. Gribble, E.T. Pelkey, W.M. Simon, H.A. Trujillo, Regioselective 1, 3-dipolar cycloaddition reactions of unsymmetrical munchnones (1, 3-oxazolium-5-olates) with 2-and 3-nitroindoles. A new synthesis of pyrrolo 3, 4-b indoles, Tetrahedron 56(2000) 10133-10140;
  (c) B. Biolatto, M. Kneeteman, E. Paredes, P.M.E. Mancini, Reactions of 1-tosyl-3-substituted indoles with conjugated dienes under thermal and/or highpressure conditions, J. Org. Chem. 66(2001) 3906-3912;
  (d) T.L.S. Kishbaugh, G.W. Gribble, Diels-Alder reactions of 2-and 3-nitroindoles. A simple hydroxycarbazole synthesis, Tetrahedron Lett. 42(2001) 4783-4785;
  (e) I. Chataigner, S.R. Piettre, Multicomponent domino[4+2]/[3+2] cycloadditions of nitroheteroaromatics:an efficient synthesis of fused nitrogenated polycycles, Org. Lett. 9(2007) 4159-4162;
  (f) S. Roy, T.L.S. Kishbaugh, J.P. Jasinski, G.W. Gribble, 1, 3-Dipolar cycloaddition of 2-and 3-nitroindoles with azomethine ylides. A new approach to pyrrolo 3, 4-b indoles, Tetrahedron Lett. 48(2007) 1313-1316;
  (g) M. Victoria Gomez, A.I. Aranda, A. Moreno, et al., Microwave-assisted reactions of nitroheterocycles with dienes. Diels-Alder and tandem hetero Diels-Alder/[3, 3] sigmatropic shift, Tetrahedron 65(2009) 5328-5336;
  (h) S. Lee, S. Diab, P. Queval, et al., Aromatic C=C bonds as dipolarophiles:facile reactions of uncomplexed electron-deficient benzene derivatives and other aromatic rings with a non-stabilized azomethine ylide, Chem. Eur. J. 19(2013) 7181-7192;
  (i) M. Andreini, M. De Paolis, I. Chataigner, Thiourea-catalyzed dearomatizing[4+2] cycloadditions of 3-nitroindole, Catal. Commun. 63(2015) 15-20.
5. [5]
  Awata A., Arai T.. PyBidine/copper catalyst. Asymmetric exo0-selective[3+2] cycloaddition using imino ester and electrophilic indole[J]. Angew. Chem. Int. Ed., 2014,53:10462-10465. doi: 10.1002/anie.201405223
6. [6]
  (a) J.Q. Zhao, Z.J. Wu, M.Q. Zhou, et al., Zn-catalyzed diastereo-and enantioselective cascade reaction of 3-isothiocyanato oxindoles and 3-nitroindoles:stereocontrolled syntheses of polycyclic spirooxindoles, Org. Lett. 17(2015) 5020-5023;
  (b) J.Q. Zhao, M.Q. Zhou, Z.J. Wu, et al., Asymmetric Michael/cyclization cascade reaction of 3-isothiocyanato oxindoles and 3-nitroindoles with amino-thiocarbamate catalysts:enantioselective synthesis of polycyclic spirooxindoles, Org. Lett. 17(2015) 2238-2241.
7. [7]
  (a) B. Dayde-Cazals, B. Fauvel, M. Singer, et al., Rational design, synthesis, and biological evaluation of 7-azaindole derivatives as potent focused multitargeted kinase inhibitors, J. Med. Chem. 59(2016) 3886-3905;
  (b) S.B. Dongare, H.V. Chavan, D.N. Surwase, et al., Indium trichloride (InCl3) catalyzed synthesis of fused 7-azaindole derivatives using domino Knoevenagel-Michael reaction, J. Chin. Chem. Soc. 63(2016) 323-330;
  (c) Q. He, G. Zhan, W. Du, Y.C. Chen, Application of 7-azaisatins in enantioselective Morita-Baylis-Hillman reaction, Beilstein J. Org. Chem. 12(2016) 309-313;
  (d) S.S. Li, H. Lin, C.F. Liu, et al., Rhodium-catalyzed tandem annulation reactions of 7-azaindoles with electron-deficient olefins via double C-H activation, Adv. Synth. Catal. 358(2016) 1595-1601;
  (e) B. Liu, R.D. Li, W. Zhan, et al., Rh (Ⅲ)-catalyzed C-H oxidative orthoolefination of arenes using 7-azaindole as a directing group and utilization in the construction of new tetracyclic heterocycles containing a 7-azaindole skeleton, RSC Adv. 6(2016) 48205-48211;
  (f) S. Rekulapally, R. Jarapula, K. Gangarapu, S. Manda, J.R. Vaidya, In silico and in vitro studies of novel 7-azaindole and 7-azaisatin derivatives as potent anticancer agents, Med. Chem. Res. 24(2015) 3412-3422;
  (g) E.R. Wood, L. Kuyper, K.G. Petrov, et al., Discovery and in vitro evaluation of potent TrkA kinase inhibitors:oxindole and aza-oxindoles, Bioorg. Med. Chem. Lett. 14(2004) 953-957;
  (h) N.M. Barl, E. Sansiaume-Dagousset, K. Karaghiosoff, P. Knochel, Full functionalization of the 7-azaindole scaffold by selective metalation and sulfoxide/magnesium exchange, Angew. Chem. Int. Ed. 52(2013) 10093-10096.
8. [8]
  (a) P. Xie, Y. Huang, Morita-Baylis-Hillman adduct derivatives (MBHADs):versatile reactivity in lewis base-promoted annulation, Org. Biomol. Chem. 13(2015) 8578-8595;
  (b) Y. Wei, M. Shi, Recent advances in organocatalytic asymmetric Morita-Baylis-Hillman/aza-Morita-Baylis-Hillman reactions, Chem. Rev. 113(2013) 6659-6690;
  (c) R. Rios, Organocatalytic enantioselective methodologies using Morita-Baylis-Hillman carbonates and acetates, Catal. Sci. Technol. 2(2012) 267-278;
  (d) T.Y. Liu, M. Xie, Y.C. Chen, Organocatalytic asymmetric transformations of modified Morita-Baylis-Hillman adducts, Chem. Soc. Rev. 41(2012) 4101-4112.
9. [9]
  (a) G.Y. Ran, P. Wang, W. Du, Y.C. Chen, α-Regioselective[3+2] annulations with Morita-Baylis-Hillman carbonates of isatins and 2-nitro-1, 3-enynes, Org. Chem. Front. 3(2016) 861-864;
  (b) K.K. Wang, T. Jin, X. Huang, et al., α-Regioselective asymmetric[3+2] annulations of Morita-Baylis-Hillman carbonates with cyclic 1-azadienes and mechanism elucidation, Org. Lett. 18(2016) 872-875.
10. [10]
  Peng J., Ran G.Y., Du W., Chen Y.C.. Tertiary-amine-catalyzed asymmetric[3+2] annulations of Morita-Baylis-Hillman carbonates of isatins with nitroolefins to construct spirooxindoles[J]. Synthesis, 2015,47:2538-2544. doi: 10.1055/s-00000084
11. [11]
  Zhan G., Shi M.L., He Q.. Catalyst-controlled switch in chemo-and diastereoselectivities:annulations of Morita-Baylis-Hillman carbonates from isatins[J]. Angew. Chem. Int. Ed., 2016,55:2147-2151. doi: 10.1002/anie.201510825
12. [12]
  Guan X.Y., Wei Y., Shi M.. Phosphine-catalyzed tandem reaction of allenoates with nitroalkenes[J]. Org. Lett., 2010,12:5024-5027. doi: 10.1021/ol102191p
1. [1]
  Qiuyun Li , Yannan Zhu , Yining Wang , Gang Qi , Wen-Juan Hao , Kelu Yan , Bo Jiang . Catalytic CH activation-initiated transdiannulation: An oxygen transfer route to ring-fluorinated tricyclic γ-lactones. Chinese Chemical Letters, 2024, 35(9): 109494-. doi: 10.1016/j.cclet.2024.109494
2. [2]
  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
3. [3]
  Danqing Wu , Jiajun Liu , Tianyu Li , Dazhen Xu , Zhiwei Miao . Research Progress on the Simultaneous Construction of C—O and C—X Bonds via 1,2-Difunctionalization of Olefins through Radical Pathways. University Chemistry, 2024, 39(11): 146-157. doi: 10.12461/PKU.DXHX202403087
4. [4]
  Yaqin Zheng , Lian Zhuo , Meng Li , Chunying Rong . Enhancing Understanding of the Electronic Effect of Substituents on Benzene Rings Using Quantum Chemistry Calculations. University Chemistry, 2025, 40(3): 193-198. doi: 10.12461/PKU.DXHX202406119
5. [5]
  Hai-Yang Song , Jun Jiang , Yu-Hang Song , Min-Hang Zhou , Chao Wu , Xiang Chen , Wei-Min He . Supporting-electrolyte-free electrochemical [2 + 2 + 1] annulation of benzo[d]isothiazole 1,1-dioxides, N-arylglycines and paraformaldehyde. Chinese Chemical Letters, 2024, 35(6): 109246-. doi: 10.1016/j.cclet.2023.109246
6. [6]
  Tao Zhou , Jing Zhou , Yunyun Liu , Jie-Ping Wan , Fen-Er Chen . Transition metal-free tunable synthesis of 3-(trifluoromethylthio) and 3-trifluoromethylsulfinyl chromones via domino C–H functionalization and chromone annulation of enaminones. Chinese Chemical Letters, 2024, 35(11): 109683-. doi: 10.1016/j.cclet.2024.109683
7. [7]
  Ke Zhang , Sheng Zuo , Pengyuan You , Tong Ru , Fen-Er Chen . Palladium-catalyzed stereoselective decarboxylative [4 + 2] cyclization of 2-methylidenetrimethylene carbonates with pyrrolidone-derived enones: Straightforward access to chiral tetrahydropyran-fused spiro-pyrrolidine-2,3-diones. Chinese Chemical Letters, 2024, 35(6): 109157-. doi: 10.1016/j.cclet.2023.109157
8. [8]
  Jindian Duan , Xiaojuan Ding , Pui Ying Choy , Binyan Xu , Luchao Li , Hong Qin , Zheng Fang , Fuk Yee Kwong , Kai Guo . Oxidative spirolactonisation for modular access of γ-spirolactones via a radical tandem annulation pathway. Chinese Chemical Letters, 2024, 35(10): 109565-. doi: 10.1016/j.cclet.2024.109565
9. [9]
  Juan Guo , Mingyuan Fang , Qingsong Liu , Xiao Ren , Yongqiang Qiao , Mingju Chao , Erjun Liang , Qilong Gao . Zero thermal expansion in Cs₂W₃O₁₀. Chinese Chemical Letters, 2024, 35(7): 108957-. doi: 10.1016/j.cclet.2023.108957
10. [10]
  Guang Xu , Cuiju Zhu , Xiang Li , Kexin Zhu , Hao Xu . Copper-catalyzed asymmetric [4+1] annulation of yne–allylic esters with pyrazolones. Chinese Chemical Letters, 2025, 36(4): 110114-. doi: 10.1016/j.cclet.2024.110114
11. [11]
  Haojie Duan , Hejingying Niu , Lina Gan , Xiaodi Duan , Shuo Shi , Li Li . Reinterpret the heterogeneous reaction of α-Fe₂O₃ and NO₂ with 2D-COS: The role of SDS, UV and SO₂. Chinese Chemical Letters, 2024, 35(6): 109038-. doi: 10.1016/j.cclet.2023.109038
12. [12]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
13. [13]
  Zizhuo Liang , Fuming Du , Ning Zhao , Xiangxin Guo . Revealing the reason for the unsuccessful fabrication of Li3Zr2Si2PO12 by solid state reaction. Chinese Journal of Structural Chemistry, 2023, 42(11): 100108-100108. doi: 10.1016/j.cjsc.2023.100108
14. [14]
  Renshu Huang , Jinli Chen , Xingfa Chen , Tianqi Yu , Huyi Yu , Kaien Li , Bin Li , Shibin Yin . Synergized oxygen vacancies with Mn2O3@CeO2 heterojunction as high current density catalysts for Li–O2 batteries. Chinese Journal of Structural Chemistry, 2023, 42(11): 100171-100171. doi: 10.1016/j.cjsc.2023.100171
15. [15]
  Maomao Liu , Guizeng Liang , Ningce Zhang , Tao Li , Lipeng Diao , Ping Lu , Xiaoliang Zhao , Daohao Li , Dongjiang Yang . Electron-rich Ni2+ in Ni3S2 boosting electrocatalytic CO2 reduction to formate and syngas. Chinese Journal of Structural Chemistry, 2024, 43(8): 100359-100359. doi: 10.1016/j.cjsc.2024.100359
16. [16]
  Ruofan Yin , Zhaoxin Guo , Rui Liu , Xian-Sen Tao . Ultrafast synthesis of Na₃V₂(PO₄)₃ cathode for high performance sodium-ion batteries. Chinese Chemical Letters, 2025, 36(2): 109643-. doi: 10.1016/j.cclet.2024.109643
17. [17]
  Yan ZHAO , Jiaxu WANG , Zhonghu LI , Changli LIU , Xingsheng ZHAO , Hengwei ZHOU , Xiaokang JIANG . Gd³⁺-doped Sc₂W3O₁₂: Eu³⁺ red phosphor: Preparation and luminescence performance. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 461-468. doi: 10.11862/CJIC.20240316
18. [18]
  Ya-Nan Yang , Zi-Sheng Li , Sourav Mondal , Lei Qiao , Cui-Cui Wang , Wen-Juan Tian , Zhong-Ming Sun , John E. McGrady . Metal-metal bonds in Zintl clusters: Synthesis, structure and bonding in [Fe₂Sn₄Bi₈]^3– and [Cr₂Sb₁₂]^3–. Chinese Chemical Letters, 2024, 35(8): 109048-. doi: 10.1016/j.cclet.2023.109048
19. [19]
  Ping Lu , Baoyin Du , Ke Liu , Ze Luo , Abiduweili Sikandaier , Lipeng Diao , Jin Sun , Luhua Jiang , Yukun Zhu . Heterostructured In2O3/In2S3 hollow fibers enable efficient visible-light driven photocatalytic hydrogen production and 5-hydroxymethylfurfural oxidation. Chinese Journal of Structural Chemistry, 2024, 43(8): 100361-100361. doi: 10.1016/j.cjsc.2024.100361
20. [20]
  Jijoe Samuel Prabagar , Kumbam Lingeshwar Reddy , Dong-Kwon Lim . Visible-light responsive gold nanoparticle and nano-sized Bi2O3-x sheet heterozygote structure for efficient photocatalytic conversion of N2 to NH3. Chinese Journal of Structural Chemistry, 2025, 44(4): 100564-100564. doi: 10.1016/j.cjsc.2025.100564

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(780)
HTML views(57)

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