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CC BY-ND-NC 4.0 · Synlett 2019; 30(04): 387-392
DOI: 10.1055/s-0037-1611341
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Highly Selective Reductive Cross-Amination between Aniline or Nitroarene Derivatives and Alkylamines Catalyzed by Polysilane-Immobilized Rh/Pt Bimetallic Nanoparticles

Aya Suzuki
,
Hiroyuki Miyamura
,
Shū Kobayashi  *
Department of Chemistry, School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
› Author AffiliationsThis work was partially supported by a Grant-in-Aid for Science Research from the Japan Society for the Promotion of Science (JSPS), the Global COE Program, The University of Tokyo, Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan, and the Japan Science and Technology Agency (JST). A. S. thanks the JSPS fellowship for Japanese Junior Scientist.
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Publication History

Received: 23.08.20018

Accepted after revision: 17 October 2018

Publication Date:
18 January 2019 (online)

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Published as part of the 30 Years SYNLETT – Pearl Anniversary Issue

Abstract

Reductive cross-amination between imine intermediates generated through partial hydrogenation of aniline or nitroarene derivatives and alkylamines is an ideal method for obtaining N-alkylated cyclohexylamine derivatives; however, no such transformations have hitherto been established. Here, we report a highly selective reductive cross-amination using aniline derivatives and alkylamines catalyzed by heterogeneous Rh/Pt bimetallic nanoparticles under mild conditions. The catalyst was recovered and reused for five runs, keeping high activity. In this reaction, imine intermediates generated during the course of partial hydrogenation of aniline derivatives were trapped immediately by strongly interacting primary alkylamines with the catalyst, which caused a highly selective transformation to give the desired products, while suppressing dicyclohexylamine formation.

Key words

reductive amination - arene hydrogenation - heterogeneous catalyst - metal nanoparticle

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1611341.
  • Supporting Information
 

  • References and Notes

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