Citation: Jia Shi-Kun, Lei Yu-Bing, Song Long-Long, Liu Shun-Ying, Hu Wen-Hao. Enantioselective trapping of oxonium ylide intermediates by N-benzhydryl-α-imino ester: Synthesis of β-tetrasubstituted α-amino acids[J]. Chinese Chemical Letters, ;2017, 28(2): 213-217. doi: 10.1016/j.cclet.2016.06.053 shu

Enantioselective trapping of oxonium ylide intermediates by N-benzhydryl-α-imino ester: Synthesis of β-tetrasubstituted α-amino acids

Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, School of Chemistry and Chemical Engineering, East China Normal University, Shanghai 200062, China

Corresponding author: Liu Shun-Ying, syliu@sist.ecnu.edu.cn Hu Wen-Hao, whu@chem.ecnu.edu.cn
Received Date: 12 May 2016
Revised Date: 15 June 2016
Accepted Date: 24 June 2016
Available Online: 25 February 2016

Figures(5)

A synergistic rhodium(II)/phosphoric acid catalyzed three component reaction of 3-diazooxindoles, alcohols and N-benzhydryl-α-imino ester is developed for the efficient construction of chiral β-alkoxy C^β-tetrasubstituted α-amino acid derivatives in good yields and with excellent diastereoselectivities and high enantioselectivities. The synthetic application of the resulting products was illustrated by reducing with Pd/C under H₂ atmosphere followed reacting with CSCl₂ at room temperature to rapid afford 3-spirocyclic oxindole in a good yield with a chirality retainment. The three-component reaction is proposed to proceed through an electrophilic trapping of the oxonium ylides by N-benzhydryl-α-imino ester.
- Three-component reaction,
- Oxonium ylide,
- N-Benzhydryl-α-imino ester,
- β-Tetrasubstituted α-amino acids,
- Chiral phosphoric acid
1. [1]
  (a) J.S. Grimley, A.M. Sawayama, H. Tanaka, et al., The enantioselective synthesis of Phomopsin B, Angew. Chem. Int. Ed. 46(2007) 8157-8159;(b) S. Fustero, M. Sánchez-Roselló, V. Rodrigo, et al., Solution-, solid-phase, and fluorous synthesis of β,β-difluorinated cyclic quaternary α-amino acid derivatives:a comparative study, Chem. Eur. J. 14(2008) 7019-7029;(c) S. Yamazaki, M. Takebayashi, K. Miyazaki, Zn(OTf)2-catalyzed reactions of ethenetricarboxylates with 2-aminobenzaldehydes leading to tetrahydroquinoline derivatives, J. Org. Chem. 75(2010) 1188-1196;(d) Q. Zhang, M. Cheng, X. Hu, B.G. Li, J.X. Ji, Gold-catalyzed three-component tandem process:an efficient and facile assembly of complex butenolides from alkynes, amines, and glyoxylic acid, J. Am. Chem. Soc. 132(2010) 7256-7257.
2. [2]
  F. Formaggio, C. Baldini, V. Moretto. Preferred conformations of peptides containing tert-leucine, a stericallydemanding, lipophilic α-amino acid with a quaternary side-chain C^β atom[J]. Chem. Eur. J., 2005,11:2395-2404. doi: 10.1002/(ISSN)1521-3765
3. [3]
  E.M. Forbeck, C.D. Evans, J.A. Gilleran, P. Li, M.M. Joullie, A regio- and stereoselective approach to quaternary centers from chiral trisubstituted aziridines, J. Am. Chem. Soc. 129(2007) 14463-14469.
4. [4]
  M. Mae, H. Amii, K. Uneyama. First synthesis of 3, 3-difluoroserine and cysteine derivatives via Mg(0)-promoted selective C-F bond cleavage of trifluoromethylimines[J]. Tetrahedron Lett., 2000,41:7893-7896. doi: 10.1016/S0040-4039(00)01350-2
5. [5]
  (a) M. Duca, D.J. Maloney, M. Lodder, B. Wang, S.M. Hecht, Synthesis of bisaminoacylated pdCpAs and tandemly activated transfer RNAs, Bioorg. Med. Chem. 15(2007) 4629-4642;(b) W. Qian, J.E. Park, K.S. Lee, T.R. Burke Jr., Effects on polo-like kinase 1 polo-box domain binding affinities of peptides incurred by structural variation at the phosphoamino acid position, Bioorg. Med. Chem. 21(2013) 3996-4003.
6. [6]
  (a) D.J. Ramón, M. Yus, Asymmetric multicomponent reactions (AMCRs):the new frontier, Angew. Chem. Int. Ed. 44(2005) 1602-1634;(b) C. de Graaff, E. Ruijter, R.V.A. Orru, Recent developments in asymmetric multicomponent reactions, Chem. Soc. Rev. 41(2012) 3969-4009;(c) P.K. Maji, R.U. Islam, S.K. Bera, Recent progress in metal assisted multicomponent synthesis of heterocycles, Heterocycles 89(2014) 869-962;(d) S.B. Dongare, H.V. Chavan, P.S. Bhale, et al., A catalyst-and solvent-free multicomponent synthesis of 7-azagramine analogues via a Mannich type reaction, Chin. Chem. Lett. 27(2016) 99-103.
7. [7]
  (a) H. Huang, X. Guo, W. Hu, Efficient trapping of oxonium ylides with imines:a highly diastereoselective three-component reaction for the synthesis of β-amino-α-hydroxyesters with quaternary stereocenters, Angew. Chem. Int. Ed. 46(2007) 1337-1339;(b) W. Hu, X. Xu, J. Zhou, et al., Cooperative catalysis with chiral Brønsted acidRh2(OAc)4:highly enantioselective three-component reactions of diazo compounds with alcohols and imines, J. Am. Chem. Soc. 130(2008) 7782-7783;(c) X. Zhang, H. Huang, X. Guo, et al., Catalytic enantioselective tapping of an alcoholic oxonium ylide with aldehydes:RhII/ZrIV-co-catalyzed three-component reactions of aryl diazoacetates, benzyl alcohol, and aldehydes, Angew. Chem. Int. Ed. 47(2008) 6647-6649;(d) X. Guan, L. Yang, W. Hu, Cooperative catalysis in multicomponent reactions:highly enantioselective synthesis of γ-hydroxyketones with a quaternary carbon stereocenter, Angew. Chem. Int. Ed. 49(2010) 2190-2192;(e) X. Guo, W. Hu, Novel multicomponent reactions via trapping of protic onium ylides with electrophiles, Acc. Chem. Res. 46(2013) 2427-2440;(f) T. Shi, X. Guo, S. Teng, W. Hu, Pd(II)-catalyzed formal[4+1] cycloaddition reactions of diazoacetates and aryl propargyl alcohols to form 2,5-dihydrofurans, Chem. Commun. 51(2015) 15204-15207;(g) M. Tang, Y. Wu, Y. Liu, et al., One-pot enantioselective multi-component cascade reactions for synthesis of chiral functionalized hydro-epoxyisochromenes:a rapid access to molecular complexity, Acta Chim. Sin. 74(2016) 54-60.
8. [8]
  (a) J. Jiang, H.D. Xu, J.B. Xi, et al., Diastereoselectively switchable enantioselective trapping of carbamate ammonium ylides with imines, J. Am. Chem. Soc. 133(2011) 8428-8431;(b) C. Jing, D. Xing, Y. Qian, et al., Diversity-oriented three-component reactions of diazo compounds with anilines and 4-oxo-enoates, Angew. Chem. Int. Ed. 52(2013) 9289-9292;(c) C. Ma, D. Xing, C. Zhai, et al., Iron porphyrin-catalyzed three-component reaction of ethyl diazoacetate with aliphatic amines and β,γ-unsaturated α-keto esters, Org. Lett. 15(2013) 6140-6143;(d) C. Jing, D. Xing, W. Hu, Highly diastereoselective synthesis of 3-hydroxy-2, 2,3-trisubstituted indolines via intramolecular trapping of ammonium ylides with ketones, Chem. Commun. 50(2014) 951-953;(e) X. Ma, J. Jiang, S. Lv, et al., An ylide transformation of rhodium(I) carbene:enantioselective three-component reaction through trapping of rhodium(I)-associated ammonium ylides by β-nitroacrylates, Angew. Chem. Int. Ed. 53(2014) 13136-13139.
9. [9]
  (a) H. Qiu, M. Li, L.Q. Jiang, et al., Highly enantioselective trapping of zwitterionic intermediates by imines, Nat. Chem. 4(2012) 733-738;(b) D. Zhang, H. Qiu, L. Jiang, et al., Enantioselective palladium(II) phosphate catalyzed three-component reactions of pyrrole, diazoesters, and imines, Angew. Chem. Int. Ed. 52(2013) 13356-13360;(c) S. Jia, D. Xing, D. Zhang, W. Hu, Catalytic asymmetric functionalization of aromatic C-H bonds by electrophilic trapping of metal-carbene-induced zwitterionic intermediates, Angew. Chem. Int. Ed. 53(2014) 13098-13101;(d) D. Zhang, J. Zhou, Z. Kang, W. Hu, Bond cleavage, fragment modification and reassembly in enantioselective three-component reactions, Nat. Commun. 6(2015) 5801-5809;(e) M. Li, X. Guo, W. Jin, et al., An enantioselective three-component reaction of diazoacetates with indoles and enals by iridium/iminium co-catalysis, Chem. Commun. 52(2016) 2736-2739;(f) H. Qiu, D. Zhang, S.Y. Liu, et al., Asymmetric C-H functionalization of indoles via enantioselective protonation, Acta Chim. Sin. 70(2012) 2484-2488.
10. [10]
  (a) B.M.Trost,L.R. Terrell,A direct catalyticasymmetricMannich-type reaction to syn-amino alcohols, J. Am. Chem. Soc. 125(2003) 338-339;(b) A. Cordova, W. Notz, G. Zhong, J.M. Betancort, C.F. Barbas, A highly enantioselective amino acid-catalyzed route to functionalized α-amino acids, J. Am. Chem. Soc. 124(2002) 1842-1843;(c) P. Ramaraju, N.A. Mir, D. Singh, et al., Enantioselective synthesis of N-PMP-1,2-dihydropyridines via formal[4+2] cycloaddition between aqueous glutaraldehyde and imines, Org. Lett. 17(2015) 5582-5585;(d) K. Nagata, Y. Kuga, A. Higashi, et al., Asymmetric synthesis and catalytic activity of 3-methyl-β-proline in enantioselective anti-Mannich-type reactions, J. Org. Chem. 78(2013) 7131-7136.
11. [11]
  (a) S. Kobayashi, R. Matsubara, Y. Nakamura, H. Kitagawa, M. Sugiura, Catalytic, asymmetric Mannich-type reactions of N-acylimino esters:reactivity, diastereoand enantioselectivity, and application to synthesis of N-acylated amino acid derivatives, J Am. Chem. Soc. 125(2003) 2507-2515;(b) D. Ferraris, B. Young, C. Cox, et al., Catalytic, enantioselective alkylation of α-imino esters:the synthesis of nonnatural α-amino acid derivatives, J. Am. Chem. Soc. 124(2002) 67-77;(c) L. Bernardi, A.S. Gothelf, R.G. Hazell, K.A. Jørgensen, Catalytic asymmetric Mannich reactions of glycine derivatives with imines. a new approach to optically active α,β-diamino acid derivatives, J. Org. Chem. 68(2003) 2583-2591.
12. [12]
  (a) S. Zhong, M. Nieger, A. Bihlmeier, M. Shi, S. Bräse, Asymmetric organocatalytic synthesis of 4,6-bis(1H-indole-3-yl)-piperidine-2 carboxylates, Org. Biomol. Chem. 12(2014) 3265-3270;(b) Y.P. He, Y.L. Du, S.W. Luo, L.Z. Gong, Asymmetric sp³ C-H functionalization via a chiral Brønsted acid-catalyzed redox reaction for the synthesis of cyclic aminals, Tetrahedron Lett. 52(2011) 7064-7066;(c) J. Jiang, X. Ma, S. Liu, et al., Enantioselective trapping of phosphoramidate ammonium ylides with imino esters for synthesis of 2,3-diaminosuccinic acid derivatives, Chem. Commun. 49(2013) 4238-4240;(d) Y. Qian, C. Jing, S. Liu, W. Hu, A highly enantioselective four-component reaction for the efficient construction of chiral β-hydroxy-α-amino acid derivatives, Chem. Commun. 49(2013) 2700-2702;(e) C. Jing, D. Xing, W. Hu, Catalytic asymmetric four-component reaction for the rapid construction of 3,3-disubstituted 3-Indol-3'-yloxindoles, Org. Lett. 17(2015) 4336-4339.
13. [13]
  (a) B.M. Trost, M.K. Brennan, Asymmetric syntheses of oxindole and indole spirocyclic alkaloid natural products, Synthesis 18(2009) 3003-3025;(b) C.V. Galliford, K.A. Schneidt, Pyrrolidinyl-spirooxindole natural products as inspirations for the development of potential therapeutic agents, Angew. Chem. Int. Ed. 46(2007) 8748-8758.
14. [14]
  D.F. Chen, F. Zhao, Y. Hu, L.Z. Gong, C-H functionalization/asymmetric Michael addition cascade enabled by relay catalysis:metal carbenoid used for C-C bond formation, Angew. Chem. Int. Ed. 53(2014) 10763-10767.
15. [15]
  L. Simón, J.M. Goodman, A model for the enantioselectivity of imine reactions catalyzed by BINOL-phosphoric acid catalysts, J. Org. Chem. 76(2011) 1775-1788.
16. [16]
  (a) X. Jiang, Y. Cao, Y. Wang, et al., A unique approach to the concise synthesis of highly optically active spirooxazolines and the discovery of a more potent oxindole-type phytoalexin analogue, J. Am. Chem. Soc. 132(2010) 15328-15333;(b) M. Suchy, P. Kutschy, K. Monde, et al., Synthesis, absolute configuration, and enantiomeric enrichment of a cruciferous oxindole phytoalexin, (S)-(-)-spirobrassinin, and its oxazoline analog, J. Org. Chem. 66(2001) 3940-3947.
1. [1]
  Bowen Wang , Longwu Sun , Qianqian Cao , Xinzhi Li , Jianai Chen , Shizhao Wang , Miaolin Ke , Fener Chen . Cu-catalyzed three-component CSP coupling for the synthesis of trisubstituted allenyl phosphorothioates. Chinese Chemical Letters, 2024, 35(12): 109617-. doi: 10.1016/j.cclet.2024.109617
2. [2]
  Yu-Hang Miao , Zheng-Xu Zhang , Xu-Yi Huang , Yuan-Zhao Hua , Shi-Kun Jia , Xiao Xiao , Min-Can Wang , Li-Ping Xu , Guang-Jian Mei . Catalytic asymmetric dearomative azo-Diels–Alder reaction of 2-vinlyindoles. Chinese Chemical Letters, 2024, 35(4): 108830-. doi: 10.1016/j.cclet.2023.108830
3. [3]
  Zhen Liu , Zhi-Yuan Ren , Chen Yang , Xiangyi Shao , Li Chen , Xin Li . Asymmetric alkenylation reaction of benzoxazinones with diarylethylenes catalyzed by B(C₆F₅)₃/chiral phosphoric acid. Chinese Chemical Letters, 2024, 35(5): 108939-. doi: 10.1016/j.cclet.2023.108939
4. [4]
  Chuan-Zhi Ni , Ruo-Ming Li , Fang-Qi Zhang , Qu-Ao-Wei Li , Yuan-Yuan Zhu , Jie Zeng , Shuang-Xi Gu . A chiral fluorescent probe for molecular recognition of basic amino acids in solutions and cells. Chinese Chemical Letters, 2024, 35(10): 109862-. doi: 10.1016/j.cclet.2024.109862
5. [5]
  Xinghui Yao , Zhouyu Wang , Da-Gang Yu . Sustainable electrosynthesis: Enantioselective electrochemical Rh(III)/chiral carboxylic acid-catalyzed oxidative CH cyclization coupled with hydrogen evolution reaction. Chinese Chemical Letters, 2024, 35(9): 109916-. doi: 10.1016/j.cclet.2024.109916
6. [6]
  Chong Liu , Ling Li , Jiahui Gao , Yanwei Li , Nazhen Zhang , Jing Zang , Cong Liu , Zhaopei Guo , Yanhui Li , Huayu Tian . The study of antibacterial activity of cationic poly(β-amino ester) regulating by amphiphilic balance. Chinese Chemical Letters, 2025, 36(2): 110118-. doi: 10.1016/j.cclet.2024.110118
7. [7]
  Long TANG , Yaxin BIAN , Luyuan CHEN , Xiangyang HOU , Xiao WANG , Jijiang WANG . Syntheses, structures, and properties of three coordination polymers based on 5-ethylpyridine-2,3-dicarboxylic acid and N-containing ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1975-1985. doi: 10.11862/CJIC.20240180
8. [8]
  Zhen Dai , Linzhi Tan , Yeyu Su , Kerui Zhao , Yushun Tian , Yu Liu , Tao Liu . Site-specific incorporation of reduction-controlled guest amino acids into proteins for cucurbituril recognition. Chinese Chemical Letters, 2024, 35(5): 109121-. doi: 10.1016/j.cclet.2023.109121
9. [9]
  Xiang Huang , Dongzhen Xu , Yang Liu , Xia Huang , Yangfan Wu , Dongmei Fang , Bing Xia , Wei Jiao , Jian Liao , Min Wang . Asymmetric synthesis of difluorinated α-quaternary amino acids (DFAAs) via Cu-catalyzed difluorobenzylation of aldimine esters. Chinese Chemical Letters, 2024, 35(12): 109665-. doi: 10.1016/j.cclet.2024.109665
10. [10]
  Qian Ren , Xue Dai , Ran Cen , Yang Luo , Mingyang Li , Ziyun Zhang , Qinghong Bai , Zhu Tao , Xin Xiao . A cucurbit[8]uril-based supramolecular phosphorescent assembly: Cell imaging and sensing of amino acids in aqueous solution. Chinese Chemical Letters, 2024, 35(12): 110022-. doi: 10.1016/j.cclet.2024.110022
11. [11]
  Min-Hang Zhou , Jun Jiang , Wei-Min He . EDA-complexes-enabled photochemical synthesis of α-amino acids with imines and tetrabutylammonium oxalate. Chinese Chemical Letters, 2025, 36(1): 110446-. doi: 10.1016/j.cclet.2024.110446
12. [12]
  Ruixue Liu , Xiaobing Ding , Qiwei Lang , Gen-Qiang Chen , Xumu Zhang . Enantioselective and divergent construction of chiral amino alcohols and oxazolidin-2-ones via Ir-f-phamidol-catalyzed dynamic kinetic asymmetric hydrogenation. Chinese Chemical Letters, 2025, 36(3): 110037-. doi: 10.1016/j.cclet.2024.110037
13. [13]
  Zhili Li , Qijun Wo , Dongdong Huang , Dezhong Zhou , Lei Guo , Yeqing Mao . Improving gene transfection efficiency of highly branched poly(β-amino ester)s through the in-situ conversion of inactive terminal groups. Chinese Chemical Letters, 2024, 35(8): 109737-. doi: 10.1016/j.cclet.2024.109737
14. [14]
  Yiyue Ding , Qiuxiang Zhang , Lei Zhang , Qilu Yao , Gang Feng , Zhang-Hui Lu . Exceptional activity of amino-modified rGO-immobilized PdAu nanoclusters for visible light-promoted dehydrogenation of formic acid. Chinese Chemical Letters, 2024, 35(7): 109593-. doi: 10.1016/j.cclet.2024.109593
15. [15]
  Junying LI , Xinyan CHEN , Xihui DIAO , Muhammad Yaseen , Chao CHEN , Hao WANG , Chuansong QI , Wei LI . Chiral fluorescent sensor Tb³⁺@Cd-CP based on camphoric acid for the enantioselective recognition of R- and S-propylene glycol. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2497-2504. doi: 10.11862/CJIC.20240084
16. [16]
  Huixin Chen , Chen Zhao , Hongjun Yue , Guiming Zhong , Xiang Han , Liang Yin , Ding Chen . Unraveling the reaction mechanism of high reversible capacity CuP₂/C anode with native oxidation PO_x component for sodium-ion batteries. Chinese Chemical Letters, 2025, 36(1): 109650-. doi: 10.1016/j.cclet.2024.109650
17. [17]
  Kaimin WANG , Xiong GU , Na DENG , Hongmei YU , Yanqin YE , Yulu MA . Synthesis, structure, fluorescence properties, and Hirshfeld surface analysis of three Zn(Ⅱ)/Cu(Ⅱ) complexes based on 5-(dimethylamino) isophthalic acid. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1397-1408. doi: 10.11862/CJIC.20240009
18. [18]
  Weizhong LING , Xiangyun CHEN , Wenjing LIU , Yingkai HUANG , Yu LI . Syntheses, crystal structures, and catalytic properties of three zinc(Ⅱ), cobalt(Ⅱ) and nickel(Ⅱ) coordination polymers constructed from 5-(4-carboxyphenoxy)nicotinic acid. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1803-1810. doi: 10.11862/CJIC.20240068
19. [19]
  Jing Cao , Dezheng Zhang , Bianqing Ren , Ping Song , Weilin Xu . Mn incorporated RuO₂ nanocrystals as an efficient and stable bifunctional electrocatalyst for oxygen evolution reaction and hydrogen evolution reaction in acid and alkaline. Chinese Chemical Letters, 2024, 35(10): 109863-. doi: 10.1016/j.cclet.2024.109863
20. [20]
  Shiyu Pan , Bo Cao , Deling Yuan , Tifeng Jiao , Qingrui Zhang , Shoufeng Tang . Complexes of cupric ion and tartaric acid enhanced calcium peroxide Fenton-like reaction for metronidazole degradation. Chinese Chemical Letters, 2024, 35(7): 109185-. doi: 10.1016/j.cclet.2023.109185

Get Citation

PDF

XML

Metrics

PDF Downloads(3)
Abstract views(691)
HTML views(28)

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