Abstract
We describe here reactions in which a carbonyl oxygen atom initiates cascade reactions by nucleophilic attack on a covalently attached benzyne. The benzynes are produced by thermal cyclization of triynes via hexadehydro-Diels–Alder reaction. The initially produced oxocarbenium/aryl carbanionic zwitterion is protonated in situ by an external protic nucleophile (NuH) of appropriate acidity. The resulting ion pair (oxocarbenium+/Nu–) collapses through several different mechanistic manifolds, adding to the diversity of structural classes that can be generated.
Original language | English (US) |
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Pages (from-to) | 425-429 |
Number of pages | 5 |
Journal | Organic Letters |
Volume | 24 |
Issue number | 1 |
DOIs | |
State | Published - Jan 14 2022 |
Bibliographical note
Funding Information:This investigation was made possible with the support of the National Institutes of General Medical Sciences of the U.S. Department of Health and Human Services (R35 GM127097). Some of the NMR data were obtained using instrumentation funded by a National Institutes of Health Shared Instrumentation Grant (S10OD011952). Mass spectrometry was performed at the University of Minnesota, Masonic Cancer Center, Analytical Biochemistry Shared Resource laboratory, using instrumentation partially funded by a Cancer Center Support Grant (CA-77598). DFT calculations were performed using resources made available through the University of Minnesota Supercomputer Institute.
Publisher Copyright:
© 2021 American Chemical Society.