On the unexpected formation of [2.2.1]- and [2.1.1]homotriblattanes
A new class of polycyclic caged compounds, the [2.n.1]homotriblattanes, is described herein. These scaffolds are accessed through a concise, three-step sequence featuring an unexpected radical cyclization of α-bromocyclopropyl ketones. Their structures and stereochemical assignments were confirmed by a combination of 2D NMR and X-ray crystallography. DFT studies provide mechanistic insight into their formation and the side products formed en route. This study expands the known chemical space of polycyclic cages and offers a new entry point into highly complex 3-dimensional frameworks.
Authors
- Hanh Thuy Nguyen (ORCID: https://orcid.org/0000-0001-7564-2428)
- Christopher D. Vanderwal (ORCID: https://orcid.org/0000-0001-7218-4521)
- Adrian E. Samkian (ORCID: https://orcid.org/0000-0002-0068-3572)
- Brian M. Stoltz (ORCID: https://orcid.org/0000-0001-9837-1528)
Institutions
- California Institute of Technology (US)
- University of California, Irvine (US)
Publication Details
- Journal
- Tetrahedron Letters
- Published
- 2025-04-01
- DOI
- https://doi.org/10.1016/j.tetlet.2025.155591
- Primary Topic
- Molecular spectroscopy and chirality
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- National Science Foundation
- University of Denver
- Beckman Institute, California Institute of Technology
- National Institute of General Medical Sciences