Citation: Chun-Hua Lu, Sima Darvishi, Vahid Khakyzadeh, Changkun Li. Pd-Catalyzed enantioselective synthesis of 2-methyl-3-methyleneindoline[J]. Chinese Chemical Letters, ;2021, 32(1): 405-407. doi: 10.1016/j.cclet.2020.02.056 shu

Pd-Catalyzed enantioselective synthesis of 2-methyl-3-methyleneindoline

a.
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
b.
Department of Applied Chemistry, K. N. Toosi University of Technology, Tehran, Iran

chkli@sjtu.edu.cn

Received Date: 8 January 2020
Revised Date: 21 February 2020
Accepted Date: 28 February 2020
Available Online: 29 February 2020

Figures(5)

A Pd-catalyzed enantioselective synthesis of 2-methyl-3-methyleneindoline in up to 89% yield and 84% ee from racemic vinyl benzoxazinanones has been developed with the help of (R,R)-BenzP^* ligand. Mechanism studies support the formation of palladacyclobutane as the key intermediate via C2 attack to π-allyl Pd complex. The β-hydride elimination provides a new reaction pathway for the palladacyclobutane.
- Palladium,
- Asymmetric catalysis,
- Vinyl benzoxazinanone,
- 2-Methyl-3-methyleneindoline,
- Palladacyclobutane
1. [1]
  (a) C. Wang, J.A. Tunge, Org. Lett. 8 (2006) 3211-3214;
  (b) C. Wang, J.A. Tunge, J. Am. Chem. Soc. 130 (2008) 8118-8119.
2. [2]
  (a) T.R. Li, F. Tan, L.Q. Lu, et al., Nat. Commun. 5 (2014) 5500;
  (b) Q. Wang, X. Qi, L.Q. Lu, et al., Angew. Chem. Int. Ed. 55 (2016) 2840-2844.
3. [3]
  (a) C. Wang, N. Pahadi, J.A. Tunge, Tetrahedron 65 (2009) 5102-5109;
  (b) G.J. Mei, C.Y. Bian, G.H. Li, et al., Org. Lett. 19 (2017) 3219-3222;
  (c) L.A. Leth, F. Glaus, M. Meazza, et al., Angew. Chem. Int. Ed. 55 (2016) 15272-15276;
  (d) Y. Wei, L.Q. Lu, T.R. Li, et al., Angew. Chem. Int. Ed. 55 (2016) 2200-2204;
  (e) M.M. Li, Y. Wei, J. Liu, et al., J. Am. Chem. Soc. 139 (2017) 14707-14713.
4. [4]
  (a) C. Guo, M. Fleige, D. Janssen-Müller, C.G. Daniliuc, F. Glorius, J. Am. Chem. Soc. 138 (2016) 7840-7843;
  (b) C. Guo, D. Janssen-Müller, M. Fleige, et al., J. Am. Chem. Soc. 139 (2017) 4443-4451.
5. [5]
  (a) L.S. Hegedus, W.H. Darlington, C.E. Russell, J. Org. Chem. 45 (1980) 5193-5196;
  (b) H.M.R. Hoffmann, A.R. Otte, A. Wilde, S. Menzer, D.J. Williams, Angew. Chem. Int. Ed. 34 (1995) 100-102.
6. [6]
  (a) A. Satake, T. Nakata, J. Am. Chem. Soc. 120 (1998) 10391-10396;
  (b) A. Satake, H. Kadohama, H. Koshino, T. Nakata, Tetrahedron Lett. 40 (1999) 3597-3600;
  (c) R. Shintani, S. Park, T. Hayashi, J. Am. Chem. Soc. 129 (2007) 14866-14867;
  (d) W. Liu, D. Chen, X.Z. Zhu, X.L. Wan, X.L. Hou, J. Am. Chem. Soc. 131 (2009) 8734-8735;
  (e) R. Shintani, T. Tsuji, S. Park, T. Hayashi, J. Am. Chem. Soc. 132 (2010) 7508-7513;
  (f) R. Shintani, K. Moriya, T. Hayashi, Chem. Commun. 47 (2011) 3057-3059;
  (g) R. Shintani, T. Ito, M. Nagamoto, H. Otomo, T. Hayashi, Chem. Commun. 48 (2012) 9936-9938;
  (h) R. Shintani, T. Ito, T. Hayashi, Org. Lett. 14 (2012) 2410-2413;
  (i) J.Q. Huang, C.H. Ding, X.L. Hou, J. Org. Chem. 79 (2014) 12010-12017;
  (j) J.Q. Huang, W. Liu, B.H. Zheng, et al., ACS Catal. 8 (2018) 1964-1972;
  (k) G.P. Zhang, S. Huang, Y.J. Jiang, et al., Chem. Commun. 55 (2019) 6449-6452.
7. [7]
  S. Duan, B. Cheng, X. Duan, et al., Org. Lett. 20 (2018) 1417-1420. doi: 10.1021/acs.orglett.8b00192
8. [8]
  N. Punna, K. Harada, J. Zhou, N. Shibata, Org. Lett. 21 (2019) 1515-1520. doi: 10.1021/acs.orglett.9b00330
9. [9]
  (a) R.C. Larock, J.M. Zenner, J. Org. Chem. 60 (1995) 482-483;
  (b) J.M. Zenner, R.C. Larock, J. Org. Chem. 64 (1999) 7312-7322;
  (c) W. Shu, Q. Yu, S. Ma, Adv. Synth. Catal. 351 (2009) 2807-2810.
1. [1]
  Xiaohui Fu , Yanping Zhang , Juan Liao , Zhen-Hua Wang , Yong You , Jian-Qiang Zhao , Mingqiang Zhou , Wei-Cheng Yuan . Palladium-catalyzed enantioselective decarboxylation of vinyl cyclic carbamates: Generation of amide-based aza-1,3-dipoles and application to asymmetric 1,3-dipolar cycloaddition. Chinese Chemical Letters, 2024, 35(12): 109688-. doi: 10.1016/j.cclet.2024.109688
2. [2]
  Zhao Gu , Yunhui Yang , Song Ye , Congyang Wang . 2,3-Arylacylation of allenes through synergetic catalysis of palladium and N-heterocyclic carbene. Chinese Chemical Letters, 2025, 36(5): 110334-. doi: 10.1016/j.cclet.2024.110334
3. [3]
  Hailong He , Wenbing Wang , Wenmin Pang , Chen Zou , Dan Peng . Double stimulus-responsive palladium catalysts for ethylene polymerization and copolymerization. Chinese Chemical Letters, 2024, 35(7): 109534-. doi: 10.1016/j.cclet.2024.109534
4. [4]
  Junlong Tang , Yuhan Zhao , Yangbin Jin , Liren Zhang , Yuanfang Wang , Wanqing Wu , Huanfeng Jiang . Palladium-catalyzed modular biomimetic synthesis of lignans derivatives. Chinese Chemical Letters, 2025, 36(7): 110969-. doi: 10.1016/j.cclet.2025.110969
5. [5]
  Zhirong Yang , Shan Wang , Ming Jiang , Gengchen Li , Long Li , Fangzhi Peng , Zhihui Shao . One stone three birds: Ni-catalyzed asymmetric allenylic substitution of allenic ethers, hydroalkylation of 1,3-enynes and double alkylation of enynyl ethers. Chinese Chemical Letters, 2024, 35(8): 109518-. doi: 10.1016/j.cclet.2024.109518
6. [6]
  Yuemin Chen , Yunqi Wu , Guoao Wang , Feihu Cui , Haitao Tang , Yingming Pan . Electricity-driven enantioselective cross-dehydrogenative coupling of two C(sp³)-H bonds enabled by organocatalysis. Chinese Chemical Letters, 2024, 35(9): 109445-. doi: 10.1016/j.cclet.2023.109445
7. [7]
  Yanxin Jiang , Kwai Wun Cheng , Zhiping Yang , Jun (Joelle) Wang . Pd-catalyzed enantioselective and regioselective asymmetric hydrophosphorylation and hydrophosphinylation of enynes. Chinese Chemical Letters, 2025, 36(5): 110231-. doi: 10.1016/j.cclet.2024.110231
8. [8]
  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
9. [9]
  Ji-Jia Zhou , Li-Gao Liu , Zhen-Tao Zhang , Hao-Xuan Dong , Xin Lu , Zhou Xu , Xin-Qi Zhu , Bo Zhou , Long-Wu Ye . Copper-catalyzed asymmetric cascade diyne cyclization/Meinwald rearrangement. Chinese Chemical Letters, 2025, 36(9): 110870-. doi: 10.1016/j.cclet.2025.110870
10. [10]
  Peng Jin , Sili Lin , Dongmei Wang , Jinsong Fan , Qingyun Liu , Kun Li . Valence-band hybridization endows the reaction specificity of AgPd nanozyme for exclusive peroxidase mimicking and improved sensing performance. Chinese Chemical Letters, 2025, 36(11): 110916-. doi: 10.1016/j.cclet.2025.110916
11. [11]
  Yan-Bo Li , Yi Li , Liang Yin . Copper(Ⅰ)-catalyzed diastereodivergent construction of vicinal P-chiral and C-chiral centers facilitated by dual "soft-soft" interaction. Chinese Chemical Letters, 2024, 35(7): 109294-. doi: 10.1016/j.cclet.2023.109294
12. [12]
  Xingfen Huang , Jiefeng Zhu , Chuan He . Catalytic enantioselective N-silylation of sulfoximine. Chinese Chemical Letters, 2024, 35(4): 108783-. doi: 10.1016/j.cclet.2023.108783
13. [13]
  Chengyao Zhao , Jingyuan Liao , Yuxiang Zhu , Yiying Zhang , Lianjie Zhai , Junrong Huang , Hengzhi You . Polystyrene-supported phosphoric-acid catalyzed atroposelective construction of axially chiral N-aryl benzimidazoles. Chinese Chemical Letters, 2025, 36(6): 110337-. doi: 10.1016/j.cclet.2024.110337
14. [14]
  Kai Zhu , Lei Yang , Yang Yang , Yanqi Wu , Fengzhi Zhang . Recent advances toward the catalytic enantioselective synthesis of planar chiral cyclophanes. Chinese Chemical Letters, 2025, 36(7): 110678-. doi: 10.1016/j.cclet.2024.110678
15. [15]
  Jun Liu , Zhaoyu Feng , Renming Pan , Xiaolong Yu , Meijuan Zhou , Gang Zhao , Hongyu Wang . Enantioselective regulation to coronal polyheterocyclic compounds via phosphonium salt-catalyzed cycloadditions of azomethine imines with γ-butenolides. Chinese Chemical Letters, 2025, 36(8): 110647-. doi: 10.1016/j.cclet.2024.110647
16. [16]
  Guodong Wang , Mengying Jia , Haitao Liu , Yong Liu , Zhiguo Zhang , Xianxiu Xu . Expeditious synthesis and applications of isoquinoline ring-modified Quinap derivatives. Chinese Chemical Letters, 2025, 36(8): 110705-. doi: 10.1016/j.cclet.2024.110705
17. [17]
  Bingbing Dong , Junmin Zhang , Xiang-Yu Ye , Xuan Huang , Yonggui Robin Chi . Catalytic construction of P-stereogenic center via phosphorus-centered nucleophilic substitution. Chinese Chemical Letters, 2025, 36(9): 111052-. doi: 10.1016/j.cclet.2025.111052
18. [18]
  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
19. [19]
  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
20. [20]
  Dan Liu . 可见光-有机小分子协同催化的不对称自由基反应研究进展. University Chemistry, 2025, 40(6): 118-128. doi: 10.12461/PKU.DXHX202408101

Get Citation

PDF

XML

Metrics

PDF Downloads(7)
Abstract views(1620)
HTML views(168)

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