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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: xinchen@cczu.edu.cn
› 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)

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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

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1611740.
  • Supporting Information
 

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