Methyleneaziridines: Unusual Vehicles for Organic Synthesis

Shipman, Michael

doi:10.1055/s-2006-951566

Cited by 38 publications

(17 citation statements)

References 34 publications

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“…Cycloaddition reactions of aziridines under thermal and photochemical conditions usually depend on the formation of reactive species before the addition event, such as 1) azomethine ylides resulting from the cleavage of a C−C bond in the aziridine ring, 2) zwitterionic 1,3‐dipoles from the cleavage of C−N bond, 3) aziridinium ions from reaction on the nitrogen, and 4) metalla‐azetidines from the oxidative addition to a metal (Figure S1 in the Supporting Information) . For the first two cases, the formation of reactive species necessitates reversible bond cleavage in the ring structure, which is evidenced by cis – trans isomerization of aziridine, often inducing undesirable side reactions…”

Section: Figurementioning

confidence: 99%

Mechanical Force Induces Ylide‐Free Cycloaddition of Nonscissible Aziridines

Jung

Yoon

2020

Angewandte Chemie

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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 nonvulnerable chemical structure can be a mechanophore.

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Section: Figurementioning

confidence: 99%

Mechanical Force Induces Ylide‐Free Cycloaddition of Nonscissible Aziridines

Jung

Yoon

2020

Angewandte Chemie

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“…cycloaddition of aziridine in the ring structure typically involve C-C or C-N bond cleavage to yield reactive intermediates such as azomethine ylides, [32][33][34] zwitterionic 1,3-dipoles, 35 aziridinium ions, 36 and metalla-azetidines, 37 prior to the addition event. In the absence of adducts such as Lewis or Brønsted acid, electrophile, or transition-metal catalyst, the formation of the azomethine ylide is a key, rate-determining step for the cycloaddition of aziridine.…”

Section: Synpacts Syn Lettmentioning

confidence: 99%

Force-Induced Cycloaddition of Aziridine: Can We Force a New Route?

Jung¹,

Kim²,

Yoon³

2020

Synlett

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Cycloaddition reactions of aziridines with dipolarophiles under traditional thermal or photochemical conditions entail destructive routes to form reactive intermediates such as an azomethine ylide. This article highlights a recent study that demonstrates a cycloaddition reaction of aziridine induced by mechanical force. Experimental results suggest that the force-induced cycloaddition of aziridine with dimethyl acetylenedicarboxylate as a dipolarophile does not seem to involve an ylide, with implications for a possible new reaction route.1 Rivalry between Aziridine and Epoxide2 Mechanochemically Responsive Polymers3 Aziridine Mechanophore4 Concluding Remarks and Outlook

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“…Cycloaddition reactions of aziridines under thermal and photochemical conditions usually depend on the formation of reactive species before the addition event, such as 1) azomethine ylides resulting from the cleavage of a CÀC bond in the aziridine ring, [17] 2) zwitterionic 1,3-dipoles from the cleavage of C À N bond, [18] 3) aziridinium ions from reaction on the nitrogen, [19] and 4) metalla-azetidines from the oxidative addition to a metal ( Figure S1 in the Supporting Information). [20] For the first two cases, the formation of reactive species necessitates reversible bond cleavage in the ring structure, which is evidenced by cis-trans isomerization of aziridine, often inducing undesirable side reactions. [21] We herein show that nonactivated aziridines can act as mechanophores and likely follow an ylide-free reaction pathway.…”

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confidence: 99%