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Title: Phenanthroline-based metal–organic frameworks for Fe-catalyzed C sp3 –H amination

Abstract

We report here the synthesis of a robust and highly porous Fe-phenanthroline-based metal–organic framework (MOF) and its application in catalyzing challenging inter- and intramolecular C–H amination reactions. For the intermolecular amination reactions, a FeBr 2-metalated MOF selectively functionalized secondary benzylic and allylic C–H bonds. The intramolecular amination reactions utilizing organic azides as the nitrene source required the reduction of the FeBr 2-metalated MOF with NaBHEt 3to generate the active catalyst. For both reactions, Fe or Zr leaching was less than 0.1%, and MOFs could be recycled and reused with no loss in catalytic activity. Furthermore, MOF catalysts were significantly more active than the corresponding homogeneous analogs. This work demonstrates the great potential of MOFs in generating highly active, recyclable, and reusable earth abundant metal catalysts for challenging organic transformations.

Authors:
 [1];  [1];  [1];  [1];  [1]
  1. Department of Chemistry; University of Chicago; Chicago; USA
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
National Science Foundation (NSF)
OSTI Identifier:
1393654
Resource Type:
Journal Article
Journal Name:
Faraday Discussions
Additional Journal Information:
Journal Volume: 201; Journal Issue: 2017; Journal ID: ISSN 1359-6640
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Thacker, Nathan C., Ji, Pengfei, Lin, Zekai, Urban, Ania, and Lin, Wenbin. Phenanthroline-based metal–organic frameworks for Fe-catalyzed C sp3 –H amination. United States: N. p., 2017. Web. doi:10.1039/C7FD00030H.
Thacker, Nathan C., Ji, Pengfei, Lin, Zekai, Urban, Ania, & Lin, Wenbin. Phenanthroline-based metal–organic frameworks for Fe-catalyzed C sp3 –H amination. United States. doi:10.1039/C7FD00030H.
Thacker, Nathan C., Ji, Pengfei, Lin, Zekai, Urban, Ania, and Lin, Wenbin. Sun . "Phenanthroline-based metal–organic frameworks for Fe-catalyzed C sp3 –H amination". United States. doi:10.1039/C7FD00030H.
@article{osti_1393654,
title = {Phenanthroline-based metal–organic frameworks for Fe-catalyzed C sp3 –H amination},
author = {Thacker, Nathan C. and Ji, Pengfei and Lin, Zekai and Urban, Ania and Lin, Wenbin},
abstractNote = {We report here the synthesis of a robust and highly porous Fe-phenanthroline-based metal–organic framework (MOF) and its application in catalyzing challenging inter- and intramolecular C–H amination reactions. For the intermolecular amination reactions, a FeBr2-metalated MOF selectively functionalized secondary benzylic and allylic C–H bonds. The intramolecular amination reactions utilizing organic azides as the nitrene source required the reduction of the FeBr2-metalated MOF with NaBHEt3to generate the active catalyst. For both reactions, Fe or Zr leaching was less than 0.1%, and MOFs could be recycled and reused with no loss in catalytic activity. Furthermore, MOF catalysts were significantly more active than the corresponding homogeneous analogs. This work demonstrates the great potential of MOFs in generating highly active, recyclable, and reusable earth abundant metal catalysts for challenging organic transformations.},
doi = {10.1039/C7FD00030H},
journal = {Faraday Discussions},
issn = {1359-6640},
number = 2017,
volume = 201,
place = {United States},
year = {2017},
month = {1}
}

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