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Cycloisomerization of Alkyne‐Tethered N‐Acyloxycarbamates to 2‐ 3H Oxazolones through.pdf (5.55 MB)

Cycloisomerization of Alkyne‐Tethered N‐Acyloxycarbamates to 2‐(3H)Oxazolones through Nitrenoid‐Mediated Carboxyamidation

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posted on 2024-01-08, 17:33 authored by Siyuan Su, Tongtong Wu, Yuanzhi Xia, Donald WinkDonald Wink, Daesung LeeDaesung Lee
The cycloisomerization of alkyne-tethered N-benzoyloxycarbamates to 2-(3H)oxazolones is described. Two catalytic systems are tailored for intramolecular 5-exo-alkyne carboxyamidation and concomitant alkene isomerization. PtCl2 /CO (5 mol%, toluene, 100 °C) promotes both carboxyamidation and alkene isomerization but has a limited substrate scope. On the other hand, FeCl3 (5 mol%, CH3 CN, 100 °C) promotes carboxyamidation effectively but a cocatalyst is required for the exocyclic alkene isomerization. Thus, a two-step one-pot protocol has been developed for a broader reaction scope, which involves FeCl3 -catalyzed carboxyamidation and base-induced alkene isomerization. Crossover experiments suggest that these reactions proceed mainly through a mechanism involving acylnitrenoid intermediates rather than carbenoid intermediates.

Funding

Reactions of Arynes and Other Reactive Intermediates | Funder: National Science Foundation | Grant ID: CHE-2055055

History

Citation

Su, S., Wu, T., Xia, Y., Wink, D. J.Lee, D. (2023). Cycloisomerization of Alkyne‐Tethered N‐Acyloxycarbamates to 2‐(3H)Oxazolones through Nitrenoid‐Mediated Carboxyamidation. Chemistry - A European Journal, 29(19), e202203371-. https://doi.org/10.1002/chem.202203371

Publisher

Wiley

Language

  • en

issn

0947-6539