Asymmetric Allylic Amination of Morita–Baylis–Hillman Adducts with Simple Aromatic Amines by Nucleophilic Amine Catalysis

Shuai Zhao; Zhi-Li Chen; Xue Rui; Ming-Mei Gao; Xin Chen

doi:10.1055/s-0037-1611740

Synlett, Table of Contents

Synlett 2019; 30(06): 703-708
DOI: 10.1055/s-0037-1611740

letter

Asymmetric Allylic Amination of Morita–Baylis–Hillman Adducts with Simple Aromatic Amines by Nucleophilic Amine Catalysis

Shuai Zhao

,

Zhi-Li Chen

,

Xue Rui

,

Ming-Mei Gao

,

Xin Chen*

School of Pharmaceutical Engineering & Life Science, Changzhou University, Changzhou, 213164, P. R. of China Email: xinchen@cczu.edu.cn

› Author Affiliations

Abstract

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Abstract

Asymmetric allylic amination of Morita–Baylis–Hillman (MBH) adducts with simple aromatic amines is successfully realized by nucleophilic amine catalysis. A range of substituted α-methylene-β-arylamino esters is accessed in moderate to high yields (up to 88%) and with excellent enantioselectivities (up to 97% ee). Inorganic fluorides are found to be able to improve the enantioselectivity of the allylic amination reaction. A pyrrole-2-carboxylate and a cyclic imide are also compatible with this catalytic system. A chiral 2,3-dihydroquinolin-4-one derivative is easily obtained from the allylic amination product.

Key words

MBH adducts - aromatic amines - asymmetric allylic amination - nucleophilic amine catalysis - inorganic fluorides

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References and Notes

1a Basavaiah D, Rao AJ, Satyanarayana T. Chem. Rev. 2003; 103: 811
1b Sorbetti JM, Clary KN, Rankic DA, Wulff JE, Parvez M, Back TG. J. Org. Chem. 2007; 72: 3326
1c Declerck V, Toupet L, Martinez J, Lamaty F. J. Org. Chem. 2009; 74: 2004
1d Galeazzi R, Martelli G, Mobbili G, Orena M, Rinaldi S. Org. Lett. 2004; 6: 2571
1e Nemoto T, Fukuyama T, Yamamoto E, Tamura S, Fukuda T, Matsumoto T, Akimoto Y, Hamada Y. Org. Lett. 2007; 9: 927
1f Murru S, McGough B, Srivastava RS. Org. Biomol. Chem. 2014; 12: 9133
1g Reddy RS, Lagishetti C, Kiran IN. C, You H, He Y. Org. Lett. 2016; 18: 3818
1h Pathak R, Madapa S, Batra S. Tetrahedron 2007; 63: 451
1i Gowrisankar S, Lee HS, Kim JM, Kim JN. Tetrahedron Lett. 2008; 49: 1670

2a Wang X, Meng F, Wang Y, Han Z, Chen Y.-J, Liu L, Wang Z, Ding K. Angew. Chem. Int. Ed. 2012; 51: 9276
2b Zhou P, Liang Y, Zhang H, Jiang H, Feng K, Xu P, Wang J, Wang X, Ding K, Luo C, Liu M, Wang Y. Eur. J. Med. Chem. 2018; 144: 817
2c Liu J, Han Z, Wang X, Wang Z, Ding K. J. Am. Chem. Soc. 2015; 137: 15346
2d Zhou P, Liu Y, Zhou L, Zhu K, Feng K, Zhang H, Liang Y, Jiang H, Luo C, Liu M, Wang Y. J. Med. Chem. 2016; 59: 10329
2e Benfatti F, Cardillo G, Gentilucci L, Mosconi E, Tolomelli A. Org. Lett. 2008; 10: 2425

3a Masson G, Housseman C, Zhu J. Angew. Chem. Int. Ed. 2007; 46: 4614
3b Declerck V, Martinez J, Lamaty F. Chem. Rev. 2009; 109: 1
3c Basavaiah D, Reddy BS, Badsara SS. Chem. Rev. 2010; 110: 5447

4a Liu X, Chai Z, Zhao G, Zhu S. J. Fluorine Chem. 2005; 126: 1215
4b Shi M, Ma G.-N, Gao J. J. Org. Chem. 2007; 72: 9779
4c Liu X, Zhao J, Jin G, Zhao G, Zhua S, Wang S. Tetrahedron 2005; 61: 3841

For some recent developments on catalytic transformation of MBH adducts, see:

5a Jiang F, Luo G.-Z, Zhu Z.-Q, Wang C.-S, Mei G.-J, Shi F. J. Org. Chem. 2018; 83: 10060
5b Cheng Y, Han Y, Li P. Org. Lett. 2017; 19: 4774
5c Zhan G, Shi M.-L, He Q, Lin W.-J, Ouyang Q, Du W, Chen Y.-C. Angew. Chem. Int. Ed. 2016; 55: 2147

6a Trost BM, Crawley ML. Chem. Rev. 2003; 103: 2921
6b Lu Z, Ma S. Angew. Chem. Int. Ed. 2008; 47: 258
6c Wang Y, Zhang T, Liu L, Wang D, Chen Y. Chin. J. Chem. 2012; 30: 2641
6d Wang X, Guo P, Han Z, Wang X, Wang Z, Ding K. J. Am. Chem. Soc. 2014; 136: 405
6e Rajesh S, Banerji B, Iqbal J. J. Org. Chem. 2002; 67: 7852
6f Wang Y, Liu L, Wang D, Chen Y.-J. Org. Biomol. Chem. 2012; 10: 6908
6g Mei G.-J, Li D, Zhou G.-X, Shi Q, Cao Z, Shi F. Chem. Commun. 2017; 53: 10030
6h Lu Y.-N, Lan J.-P, Mao Y.-J, Wang Y.-X, Mei G.-J, Shi F. Chem. Commun. 2018; 54: 18527
6i Li M.-M, Wei Y, Liu J, Chen H.-W, Lu L.-Q, Xiao W.-J. J. Am. Chem. Soc. 2017; 139: 14707
6j Wang Y.-N, Wang B.-C, Zhang M.-M, Gao X.-W, Li T.-R, Lu L.-Q, Xiao W.-J. Org. Lett. 2017; 19: 4094
6k Mei G.-J, Bian C.-Y, Li G.-H, Xu S.-L, Zheng W.-Q, Shi F. Org. Lett. 2017; 19: 3219

7a Rios R. Catal. Sci. Technol. 2012; 2: 267
7b Liu T.-Y, Xie M, Chen Y.-C. Chem. Soc. Rev. 2012; 41: 4101
7c Wei Y, Shi M. Chem. Rev. 2013; 113: 6659
7d Cui H.-L, Feng X, Peng J, Lei J, Jiang K, Chen Y.-C. Angew. Chem. Int. Ed. 2009; 48: 5737
7e Zhang H, Zhang S.-J, Zhou Q.-Q, Dong L, Chen Y.-C. Beilstein J. Org. Chem. 2012; 8: 1241
7f Huang J.-R, Cui H.-L, Lei J, Sun X.-H, Chen Y.-C. Chem. Commun. 2011; 47: 4784
7g Lu H, Lin J.-B, Liu J.-Y, Xu P.-F. Chem. Eur. J. 2014; 20: 11659
7h Lin A, Mao H, Zhu X, Ge H, Tan R, Zhu C, Cheng Y. Chem. Eur. J. 2011; 17: 13676
7i Zhang S.-J, Cui H.-L, Jiang K, Li R, Ding Z.-Y, Chen Y.-C. Eur. J. Org. Chem. 2009; 5804
7j Pei C.-K, Zhang X.-C, Shi M. Eur. J. Org. Chem. 2011; 4479
7k Zhao M.-X, Chen M.-X, Tang W.-H, Wei D.-K, Dai T.-L, Shi M. Eur. J. Org. Chem. 2012; 3598
7l Sun W, Ma X, Hong L, Wang R. J. Org. Chem. 2011; 76: 7826
7m Huang L, Wei Y, Shi M. Org. Biomol. Chem. 2012; 10: 1396
7n Cho C.-W, Kong J.-R, Krische MJ. Org. Lett. 2004; 6: 1337
7o Pellissier H. Tetrahedron 2017; 73: 2831
7p Zhang T.-Z, Dai L.-X, Hou X.-L. Tetrahedron: Asymmetry. 2007; 18: 1990

8a Lee CG, Lee KY, Lee S, Kim JN. Tetrahedron 2005; 61: 1493
8b Bakthadoss M, Srinivasan J, Selvakumar R. Aust. J. Chem. 2014; 67: 295
8c Ge S.-Q, Hua Y.-Y, Xia M. Synth. Commun. 2010; 40: 1954
8d Ge S.-Q, Hua Y.-Y, Xia M. Ultrason. Sonochem. 2009; 16: 743

9a Zhao S, Lin J.-B, Zhao Y.-Y, Liang Y.-M, Xu P.-F. Org. Lett. 2014; 16: 1802
9b Zhao S, Zhao Y.-Y, Lin J.-B, Xie T, Liang Y.-M, Xu P.-F. Org. Lett. 2015; 17: 3206

10a Su W, Raders S, Verkade JG, Liao X, Hartwig JF. Angew. Chem. Int. Ed. 2006; 45: 5852
10b Bugarin A, Connell BT. Chem. Commun. 2010; 46: 2644
10c Zhu B, Yan L, Pan Y, Lee R, Liu H, Han Z, Huang K.-W, Tan C.-H, Jiang Z. J. Org. Chem. 2011; 76: 6894

11 Asymmetric Allylic Amination; General ProcedureA solution of amine 2 (0.05 mmol), MBH carbonate 3 (0.1 mmol), catalyst 1k (0.01 mmol) and CaF₂ (0.25 mmol) in p-xylene (0.5 mL) was stirred at room temperature for 72 hours. Then the reaction mixture was directly purified by flash column chromatography (eluting with EtOAc/petroleum ether, 10:1) to afford the product 4.Methyl (R)-2-[Phenyl(phenylamino)methyl]acrylate (4aa) Colorless oil; 80% yield; 92% ee; [α]_D ²⁸= –91.1 (c 0.7, CHCl₃). The enantiomeric excess was determined by HPLC analysis with an OD-H column (n-hexane/i-PrOH, 95:5), 1.0 mL/min, λ = 254 nm, t _R (major) = 8.57 min, t _R (minor) = 10.76 min. ¹H NMR (300 MHz, CDCl₃): δ = 7.40–7.28 (m, 5 H), 7.20–7.14 (m, 2 H), 6.75–6.70 (m, 1 H), 6.58 (dd, J = 8.4 Hz, J = 0.9 Hz, 2 H), 6.40 (s, 1 H), 5.97 (t, J = 1.2 Hz, 1 H), 5.41 (s, 1 H), 4.16 (s, 1 H), 3.71 (s, 3 H); ¹³C NMR (100 MHz, CDCl₃): δ = 166.8, 146.8, 140.7, 140.0, 129.3, 128.9, 128.0, 127.7, 126.4, 118.0, 113.5, 59.1, 52.1; HRMS (ESI): m/z [M + H]⁺ calcd for C₁₇H₁₈NO₂: 268.1332; found: 268.1333.

12a Wu G, Wong Y, Chen X, Ding Z. J. Org. Chem. 1999; 64: 3714
12b Sasikala CH. V. A, Padi PR, Sunkara V, Ramayya P, Dubey PK, Uppala VB. R, Praveen C. Org. Process Res. Dev. 2009; 13: 907

13a Kim JN, Lee HJ, Gong JH. Tetrahedron Lett. 2002; 43: 9141
13b Baidya M, Remennikov GY, Mayer P, Mayr H. Chem. Eur. J. 2010; 16: 1365

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