2020
DOI: 10.1002/anie.201915438
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Mechanical Force Induces Ylide‐Free Cycloaddition of Nonscissible Aziridines

Abstract: The application of aziridines as nonvulnerable mechanophores is reported. Upon exposure to a mechanical force, stereochemically pure nonactivated aziridines incorporated into the backbone of a macromolecule do not undergo cis–trans isomerization, thus suggesting retention of the ring structure under force. Nonetheless, aziridines react with a dipolarophile and seem not to obey conventional reaction pathways that involve C−C or C−N bond cleavage prior to the cycloaddition. Our work demonstrates that a nonvulner… Show more

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Cited by 29 publications
(21 citation statements)
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“…Over the last decade or so, coupled mechanical forces have been used to drive a range of targeted covalent responses in isolated polymers and in bulk polymeric materials (covalent polymer mechanochemistry). [1][2][3] Mechanochemical strategies continue to evolve, including their recent use in biasing and probing reaction pathways, 4,5 the release of small molecules and protons, [6][7][8] stress reporting, [9][10][11][12][13] stress strengthening, [14][15][16] degradable polymers, 17,18 and fundamental studies of polymer behaviour under load. 19 In organic reactions, mechanochemical coupling has been investigated in simple bond dissociation reactions [20][21][22][23][24] and in a wide variety of reaction classes with respect to regiochemistry, [25][26][27][28] orbital symmetry, 25,[29][30][31] stereochemistry, 32,33 supramolecular architecture, 34,35 dynamic effects, 36,37 and the alignment and/or loading of scissile bonds with applied tension.…”
Section: Introductionmentioning
confidence: 99%
“…Over the last decade or so, coupled mechanical forces have been used to drive a range of targeted covalent responses in isolated polymers and in bulk polymeric materials (covalent polymer mechanochemistry). [1][2][3] Mechanochemical strategies continue to evolve, including their recent use in biasing and probing reaction pathways, 4,5 the release of small molecules and protons, [6][7][8] stress reporting, [9][10][11][12][13] stress strengthening, [14][15][16] degradable polymers, 17,18 and fundamental studies of polymer behaviour under load. 19 In organic reactions, mechanochemical coupling has been investigated in simple bond dissociation reactions [20][21][22][23][24] and in a wide variety of reaction classes with respect to regiochemistry, [25][26][27][28] orbital symmetry, 25,[29][30][31] stereochemistry, 32,33 supramolecular architecture, 34,35 dynamic effects, 36,37 and the alignment and/or loading of scissile bonds with applied tension.…”
Section: Introductionmentioning
confidence: 99%
“…Over the last decade or so, coupled mechanical forces have been used to drive a range of targeted covalent responses in isolated polymers and in bulk polymeric materials (covalent polymer mechanochemistry). 1,2 Mechanochemical strategies continue to evolve, including in very recent years their use in biasing and probing reaction pathways, 3,4 the release of small molecules and protons, 5,6 stress reporting, [7][8][9][10][11] stress strengthening, 12,13 degradable polymers, 14,15 and fundamental studies of polymer behavior under load. 16 In organic reactions, mechanochemical coupling has been investigated in simple bond dissociation reactions [17][18][19] and in a wide variety of reaction classes with respect to regiochemistry, [20][21][22][23][24] orbital symmetry, 20,[25][26][27] stereochemistry, 28,29 supramolecular architecture, [30][31][32] dynamic effects, 33,34 and the alignment and/or loading of scissile bonds with applied tension.…”
Section: Introductionmentioning
confidence: 99%
“…Our group has recently probed the potential of aziridine for a mechanophore [7a] . The trivalency of nitrogen atom allows one to fine‐tune reactivity of aziridine [17] .…”
Section: Methodsmentioning
confidence: 99%