Allylsilane Reagent-Controlled Divergent Asymmetric Catalytic Reactions of 2-Naphthoquinone-1-methide

Herein, the first allylsilane reagent-controlled divergent asymmetric Hosomi–Sakurai conjugate allylation and hetero-Diels–Alder (HDA) with 2-naphthoquinone-1-methide (2-Nap-Q-1-M) under the catalysis of Sc^III/Feng ligand complex is reported. With these methods, a variety of uniquely substituted chiral allyl-functionalized diaryl compounds and naphthopyran products were obtained in a straightforward and highly stereoselective (up to 96.5:3.5 e.r.) manner under mild conditions. Moreover, it is demonstrated that 2-Nap-Q-1-M can serve as an efficient diene for a side asymmetric Diels–Alder (D-A) reaction. This principle can provide a straightforward access to hydrophenalene in an optically active form, which represents a structural core of various natural products and bioactive molecules.