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Strain‐Release Driven Epoxidation and Aziridination of Bicyclo[1.1.0]butanes via Palladium Catalyzed σ‐Bond Nucleopalladation

Strained spirocyclic epoxides and aziridines were synthesized via three-component coupling between in situ generated 1-lithio bicyclo[1.1.0]butane, a broad variety of ketones, aldehydes and N-tosyl imines, and aryl triflates. The key step involves a highly diastereoselective palladium-catalyzed C−C σ-bond alkoxyarylation (or aminoarylation) of bicyclo[1.1.0]butyl carbinolate intermediates.


The development of preparative methods for the synthesis of four-membered carbocycles is gaining increasing importance due to the widespread utility of cyclic compounds in medicinal chemistry. Herein, we report the development of a new methodology for the production of spirocyclic epoxides and aziridines containing a cyclobutane motif. In a two-step one-pot process, a bicyclo[1.1.0]butyl sulfoxide is lithiated and added to a ketone, aldehyde or imine, and the resulting intermediate is cross-coupled with an aryl triflate through C−C σ-bond alkoxy- or aminopalladation with concomitant epoxide or aziridine formation. After careful optimization, a remarkably efficient reaction was conceived that tolerated a broad variety of both aromatic and aliphatic substrates. Lastly, through several high yielding ring-opening reactions, we demonstrated the excellent applicability of the products as modular building blocks for the introduction of three-dimensional structures into target molecules.

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