Tungsten-Enabled Diels–Alder Cycloaddition and Cycloreversion of Arenes and Alkynes: Divergent Synthesis of Highly Functionalized Barrelenes and Arenes
The Diels-Alder reaction of benzenes remains a significant synthetic challenge, owing to their highly stabilized aromatic cores. In this work, the dearomatization agent {WTp(NO)(PMe<sub>3</sub>)} is used to promote Diels-Alder reactions of dihapto-coordinated (η<sup>2</sup>) benzenes with alkynes. The resulting η<sup>2</sup>-barrelene complexes can be oxidized to liberate intact barrelenes. Alternatively, mild pyrolysis leads to the extraction of the corresponding tungsten-acetylene complex and concomitant formation of new arenes possessing substituents originating from the acetylene dienophiles.
Authors
- Diane A. Dickie (ORCID: https://orcid.org/0000-0003-0939-3309)
- Megan N. Ericson (ORCID: https://orcid.org/0000-0002-1871-1252)
- Ismail Patel (ORCID: https://orcid.org/0009-0009-2465-0749)
- Jetze J. Tepe (ORCID: https://orcid.org/0000-0001-5467-5589)
- Evan Savelson (ORCID: https://orcid.org/0000-0001-8963-3071)
- Jeremy M. Bloch (ORCID: https://orcid.org/0000-0002-9372-714X)
- Alvin Q. Meng (ORCID: https://orcid.org/0009-0006-1410-5980)
- W. Dean Harman (ORCID: https://orcid.org/0000-0003-0939-6980)
Institutions
- University of Virginia (US)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2025-08-08
- DOI
- https://doi.org/10.1021/jacs.5c08320
- Citations
- 2
- Primary Topic
- Asymmetric Synthesis and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 1.87
Funders
- National Institute on Aging
- National Cancer Institute
- National Institute of General Medical Sciences
- Division of Chemistry