Chemical Consequences of the Mechanical Bond: A Tandem Active Template-Rearrangement Reaction

Florian Modicom; Ellen M.G. Jamieson; Elise Rochette; Stephen M. Goldup

doi:10.1002/anie.201813950

Chemical Consequences of the Mechanical Bond: A Tandem Active Template-Rearrangement Reaction

Florian Modicom, Ellen M.G. Jamieson, Elise Rochette, Stephen M. Goldup^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

19 Citations (Scopus)

Abstract

We report the unexpected discovery of a tandem active template CuAAC-rearrangement process, in which N ₂ is extruded on the way to the 1,2,3-triazole product to give instead acrylamide rotaxanes. Mechanistic investigations suggest this process is dictated by the mechanical bond, which stabilizes the Cu ^I -triazolide intermediate of the CuAAC reaction and diverts it down the rearrangement pathway; when no mechanical bond is formed, the CuAAC product is isolated.

Original language	English
Pages (from-to)	3875-3879
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	12
DOIs	https://doi.org/10.1002/anie.201813950
Publication status	Published - 18 Mar 2019

Bibliographical note

Funding Information:
The authors acknowledge the use of the IRIDIS High Performance Computing Facility, and associated support services at the University of Southampton. The authors thank Fluorochem for the gift of reagents. S.M.G. acknowledges funding from the European Research Council (Con- solidator Grant Agreement no. 724987), and Leverhulme Trust (ORPG-2733). S.M.G. thanks the Royal Society for a Research Fellowship. E.M.G.J. and F.M. thank the University of Southampton and EPSRC for financial support (EP/ M508147/1).

Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

mechanical bonds
rearrangement
rotaxanes
supramolecular chemistry
triazoles

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1002/anie.201813950

Cite this

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title = "Chemical Consequences of the Mechanical Bond: A Tandem Active Template-Rearrangement Reaction",

abstract = " We report the unexpected discovery of a tandem active template CuAAC-rearrangement process, in which N 2 is extruded on the way to the 1,2,3-triazole product to give instead acrylamide rotaxanes. Mechanistic investigations suggest this process is dictated by the mechanical bond, which stabilizes the Cu I -triazolide intermediate of the CuAAC reaction and diverts it down the rearrangement pathway; when no mechanical bond is formed, the CuAAC product is isolated.",

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author = "Florian Modicom and Jamieson, {Ellen M.G.} and Elise Rochette and Goldup, {Stephen M.}",

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doi = "10.1002/anie.201813950",

language = "English",

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AU - Jamieson, Ellen M.G.

AU - Rochette, Elise

AU - Goldup, Stephen M.

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KW - mechanical bonds

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KW - rotaxanes

KW - supramolecular chemistry

KW - triazoles

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Chemical Consequences of the Mechanical Bond: A Tandem Active Template-Rearrangement Reaction

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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