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.
Bibliographical noteFunding 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).
© 2022 American Chemical Society.
- Cycloaddition Reaction
PubMed: MeSH publication types
- Journal Article
- Research Support, N.I.H., Extramural
- Research Support, U.S. Gov't, Non-P.H.S.