One-Pot Preparation of Tricyclo[5.2.2.04,9]undecanes via Cu-Catalyzed Asymmetric Carboboration of Cyclohexadienone-Tethered Allenes

The Cu-catalyzed asymmetric carboboration of cyclohexadienone-tethered allenes has been achieved through regioselective beta-borylation of the allenes and subsequent conjugate addition to cyclohexadienones, affording cis-bicyclic frameworks with acceptable yields and high to excellent enantioselectivities. Further conjugate borylation of the carboboration products proved to be a favorable kinetic resolution process, which improved the overall enantioselectivity. Finally, one-pot preparation of highly enantioenriched tricyclo[5.2.2.0(4,9)]undecanes was developed from the cyclohexadienone-tethered allenes through beta-borylation/1,4-addition and subsequent tandem oxidation/intramolecular aldol reaction.

Automated summary

The study successfully achieved Cu-catalyzed asymmetric carboboration of cyclohexadienone-tethered allenes, resulting in cis-bicyclic frameworks with high enantioselectivities. Further conjugate borylation improved the overall enantioselectivity, and one-pot preparation of highly enantioenriched tricyclo[5.2.2.0(4,9)]undecanes was developed.