Jump to main content
Jump to site search

Issue 1, 2017
Previous Article Next Article

Pyramidalization/twisting of the amide functional group via remote steric congestion triggered by metal coordination

Author affiliations

Abstract

For decades, the planarity of the amide functional group has garnered sustained interest in organic chemistry, enticing chemists to deform its usually characteristic high-fidelity plane. As opposed to the construction of amides that are distorted by imposing rigid covalent bond assemblies, we demonstrate herein the deformation of the amide plane through increased steric bulk in the periphery of the amide moiety, which is induced by coordination to metal cations. A crystallographic analysis revealed that the thus obtained amides exhibit significant pyramidalization and twisting upon coordination to the metals, while the amide functional group remained intact. The observed deformation, which should be attributed to through-space interactions, substantially enhanced the solvolytic cleavage of the amide, providing compelling evidence that temporary crowding in the periphery of the amide functional group may be used to control the reactivity of amides.

Graphical abstract: Pyramidalization/twisting of the amide functional group via remote steric congestion triggered by metal coordination

Back to tab navigation
Please wait while Download options loads

Supplementary files

Publication details

The article was received on 16 Aug 2016, accepted on 21 Sep 2016 and first published on 23 Sep 2016


Article type: Edge Article
DOI: 10.1039/C6SC03669D
Citation: Chem. Sci., 2017,8, 85-90
  • Open access: Creative Commons BY license
  •   Request permissions

    Pyramidalization/twisting of the amide functional group via remote steric congestion triggered by metal coordination

    S. Adachi, N. Kumagai and M. Shibasaki, Chem. Sci., 2017, 8, 85
    DOI: 10.1039/C6SC03669D

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author