Synthesis 2020; 52(03): 393-398
DOI: 10.1055/s-0039-1690010
paper
© Georg Thieme Verlag Stuttgart · New York

Leaving Group Ability in Nucleophilic Aromatic Amination by Sodium Hydride–Lithium Iodide Composite

Jia Hao Pang
a   Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore   Email: shunsuke@ntu.edu.sg
,
Derek Yiren Ong
a   Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore   Email: shunsuke@ntu.edu.sg
,
Kohei Watanabe
b   Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan   Email: takita@mol.f.u-tokyo.ac.jp
,
Ryo Takita  ∗
b   Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan   Email: takita@mol.f.u-tokyo.ac.jp
,
Shunsuke Chiba  ∗
a   Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore   Email: shunsuke@ntu.edu.sg
› Author AffiliationsThis work was supported by funding from Nanyang Technological University (NTU) (for S.C.), the Singapore Ministry of Education (Academic Research Fund Tier 1: RG10/17 for S.C.), and Japan Society for the Promotion of Science [Grant-in-Aid for Scientific Research (C) (19K0662)], Takeda Science Foundation, The FUGAKU Trust for Medicinal Research, and Uehara Memorial Foundation (for R.T.).
Further Information

Publication History

Received: 30 June 2019

Accepted after revision: 16 July 2019

Publication Date:
24 July 2019 (online)

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Abstract

The methoxy group is generally considered as a poor leaving group for nucleophilic substitution reactions. This work verified the superior ability of the methoxy group in nucleophilic amination of arenes mediated by the sodium hydride and lithium iodide through experimental and computational approaches.

Key words

nucleophilic amination - concerted aromatic substitution - methoxy group - sodium hydride - DFT calculations

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0039-1690010.
  • Supporting Information
 

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