Synlett 2019; 30(06): 703-708
DOI: 10.1055/s-0037-1611740
letter
© Georg Thieme Verlag Stuttgart · New York

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: [email protected]
› Author Affiliations

We gratefully acknowledge the financial support from the National Science Foundation of China (21602018, 21272029) and the Jiangsu Overseas Visiting Scholar Program for University Prominent Young & Middle-Aged Teachers and Presidents.
Further Information

Publication History

Received: 14 January 2019

Accepted after revision: 04 February 2019

Publication Date:
26 February 2019 (online)


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.

Supporting Information

 
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  • 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.
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