Asymmetric higher-order [10 + n] cycloadditions of palladium-containing 10π-cycloaddends

We uncovered an asymmetric higher-order [10 + 2] cycloaddition reaction between diverse activated alkenes and a new type of π-allylpalladium complex-containing dipole-type 10π-cycloaddend, which was generated in situ from 2-methylene-1-indanols via a dehydrative insertion and deprotonation strategy under double activation of Pd(0) and phosphoric acid. A similar strategy was applied to an asymmetric higher-order [10 + 8] cycloaddition reaction or [10 + 4] cycloaddition reaction by using a heptafulvene derivative or a cyclic enone, respectively, as the acceptor. A variety of polycyclic frameworks imbedding an indene core were generally furnished in moderate to excellent yields with high levels of enantioselectivity by employing a newly designed chiral phosphoramidite ligand.

A type of π-allylpalladium complex-containing 10π-cycloaddend generated from 2-methylene-1-indanols under double activation of Pd(0) and phosphoric acid undergoes asymmetric higher-order [10 + 2] cycloadditions with diverse activated alkenes.