Enantioselective Inverse Electron Demand (3+2) Cycloaddition of Palladium-Oxyallyl Enabled by a Hydrogen-Bond-Donating Ligand

Cycloaddition reactions between oxyallyl cations and alkenes are important transformations for the construction of ring systems. Although (4 + 3) cycloaddition reactions of oxyallyl cations are well-developed, (3 + 2) cycloadditions remain rare, and an asymmetric version has not yet been developed. Moreover, because oxyallyl cations are highly electrophilic, only electron-rich olefins can be used as cycloaddition partners. We herein report a method for enantioselective (3 + 2) cycloaddition reactions between palladium-oxyallyl species and electron-deficient nitroalkenes. This transformation was enabled by a rationally designed hydrogen-bond-donating ligand (FeUrPhos) and proceeded via an inverse electron demand pathway. Using this method, we could assemble cyclopentanones with up to three contiguous stereocenters with high enantioselectivity and good to excellent diastereoselectivity.

Automated summary

This study presents a method for enantioselective (3 + 2) cycloaddition reactions between palladium-oxyallyl species and electron-deficient nitroalkenes. The transformation, enabled by a hydrogen-bond-donating ligand (FeUrPhos) and an inverse electron demand pathway, allows for the assembly of cyclopentanones with up to three contiguous stereocenters with high enantioselectivity.