SmI2-Catalyzed Coupling of Alkyl Housane Ketones and Alkenes in an Approach to Norbornanes

Debayan Roy; Jack I Mansell; Giorgia Barison; Song Yu; Rocco Katavic; Ciro Romano; Nikolas Kaltsoyannis; David John Procter

doi:10.1002/anie.202512018

SmI2-Catalyzed Coupling of Alkyl Housane Ketones and Alkenes in an Approach to Norbornanes

Angew Chem Int Ed Engl. 2025 Jul 8:e202512018. doi: 10.1002/anie.202512018. Online ahead of print.

Authors

Debayan Roy¹, Jack I Mansell¹, Giorgia Barison¹, Song Yu¹, Rocco Katavic¹, Ciro Romano¹, Nikolas Kaltsoyannis¹, David John Procter²

Affiliations

¹ The University of Manchester, Chemistry, UNITED KINGDOM OF GREAT BRITAIN AND NORTHERN IRELAND.
² The University of Manchester, School of Chemistry, Oxford Road, M13 9PL, Manchester, UNITED KINGDOM OF GREAT BRITAIN AND NORTHERN IRELAND.

PMID: 40626914
DOI: 10.1002/anie.202512018

Abstract

Cross-coupling strategies involving strain-release have gained significant recent attention for the construction of complex molecular frameworks, particularly in the context of preparing bioisosteres for medicinal chemistry. While the reactivity of cyclopropanes and bicyclo[1.1.0]butanes (BCBs) has been extensively studied, higher homologues are emerging as valuable substrates for synthesis. For example, methods for the fragmentation and coupling of bicyclo[2.1.0]pentane, or housane, ketones show promise, but are currently limited in substrate scope. Here, we describe a mild, atom-economical, samarium diiodide (SmI2) catalyzed fragmentation and coupling of alkyl and aryl housane ketones with alkenes that grants access to functionalized norbornane structural motifs, not easily accessible by classical cycloaddition approaches, and with considerable potential for further manipulation.

Keywords: Catalysis; Radicals; housane; samarium; strain release.