In Situ Allene Formation via Alkyne Tautomerization to Promote [4 + 2]-Cycloadditions with a Pendant Alkyne or Nitrile

Niklas Kraemer, Rajasekhar R Naredla, Thomas R. Hoye

Research output: Contribution to journalArticlepeer-review

Abstract

We have explored the net-[4 + 2]-cycloadditions of a variety of aryl (or alkenyl) alkynes. Tautomerization via base-catalyzed alkyne-to-allene isomerization produces a transient allene, which undergoes stepwise cyclization with not only a pendant alkyne but also a nitrile. The operative mechanisms for these reactions were studied by density functional theory and compared with the slower thermal cyclization of the precursor alkyne.

Original languageEnglish (US)
Pages (from-to)2327-2331
Number of pages5
JournalOrganic Letters
Volume24
Issue number12
DOIs
StatePublished - Apr 1 2022

Bibliographical note

Funding Information:
This research was made possible by a grant from the National Institutes of General Medical Sciences of the U.S. Department of Health and Human Services (R35 GM127097). N.K. is supported by a Graduate Research Fellowship from the National Science Foundation. NMR spectral data were collected, in part, with an instrument funded by the NIH Shared Instrumentation Grant program (S10OD011952). High-resolution mass spectra measured at the University of Minnesota Masonic Cancer Center were done using instrumentation that was partially funded by an NIH Cancer Center Support Grant (CA-77598). Computational studies were performed using software and hardware made available by the University of Minnesota Supercomputing Institute (MSI).

Publisher Copyright:
© 2022 American Chemical Society.

Keywords

  • Alkadienes
  • Alkynes
  • Catalysis
  • Cycloaddition Reaction
  • Nitriles

PubMed: MeSH publication types

  • Journal Article
  • Research Support, N.I.H., Extramural
  • Research Support, U.S. Gov't, Non-P.H.S.

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