Abstract
Polycyclic, highly fused, and, perforce, highly conjugated aromatic organic compounds have been of interest to chemists since the discovery of naphthalene in 1821. In modern decades these have attracted ever-growing attention because of their architectures, properties, and wide-ranging practical applications. Given the unabated interest in such molecules, the development of new methods and strategies for the practical synthesis of PACs having new structural motifs is important. Here, we describe one-pot, purely thermal cyclizations of substrates containing sets of independent triynes, each arrayed upon a common core structure. This produces topologically unique products through sequential generation/trapping of a series of benzyne intermediates. More specifically, these all conform to processes that can be considered as radial-hexadehydro-Diels-Alder (HDDA) reactions. The late-stage and de novo creation of multiple arenes in these multibenzyne processes constitutes a fundamentally new synthetic strategy for constructing novel molecular topologies.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 2527-2537 |
| Number of pages | 11 |
| Journal | Chem |
| Volume | 7 |
| Issue number | 9 |
| DOIs | |
| State | Published - Sep 9 2021 |
Bibliographical note
Funding Information:Support for this work was provided by the National Science Foundation (CHE-1665389). The DFT calculations were performed using software and hardware available through the University of Minnesota Supercomputing Institute (MSI). Some NMR spectral data were obtained with an instrument purchased with a grant from the NIH Shared Instrumentation Grant Program (S10OD011952). The authors thank Dr. V.G. Young, Jr. (University of Minnesota) for performing the X-ray diffraction analysis. X-ray diffraction data were collected on an instrument purchased with funds from the National Science Foundation (NSF/MRI 1229400). Mass spectrometry data were recorded in the Masonic Cancer Center at the University of Minnesota (Analytical Biochemistry Shared Resource) with instrumentation partially funded by a National Institutes of Health Cancer Center Support Grant (CA-77598). D.L. and T.R.H. co-wrote the manuscript. D.L. (Figures 2, 3, 4, and 5), S.P.R. (Figures 4A and 4B), and X.X. (Figure 4C) executed the experiments and collected and interpreted the data. All authors approved the final version of the manuscript. The authors declare no competing interests.
Funding Information:
Support for this work was provided by the National Science Foundation ( CHE-1665389 ). The DFT calculations were performed using software and hardware available through the University of Minnesota Supercomputing Institute (MSI). Some NMR spectral data were obtained with an instrument purchased with a grant from the NIH Shared Instrumentation Grant Program ( S10OD011952 ). The authors thank Dr. V.G. Young, Jr. (University of Minnesota) for performing the X-ray diffraction analysis. X-ray diffraction data were collected on an instrument purchased with funds from the National Science Foundation ( NSF/MRI 1229400 ). Mass spectrometry data were recorded in the Masonic Cancer Center at the University of Minnesota (Analytical Biochemistry Shared Resource) with instrumentation partially funded by a National Institutes of Health Cancer Center Support Grant ( CA-77598 ).
Publisher Copyright:
© 2021 Elsevier Inc.
Keywords
- HDDA
- SDG7: Affordable and clean energy
- aryne
- hexadehydro-Diels-Alder
- multi-yne
- multiple cycloisomerizations