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 ScIII/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. Asymmetric catalytic reactions: The first allylsilane reagent‐controlled divergent asymmetric Hosomi–Sakurai conjugate allylation and hetero‐Diels–Alder reaction with 2‐naphthoquinone‐1‐methide (2‐Nap‐Q‐1‐M) under the catalysis of ScIII/Feng ligand complex is reported. Moreover, 2‐Nap‐Q‐1‐M can serve as an efficient diene for a side asymmetric Diels–Alder reaction, which provides access to chiral hydrophenalene, representing a structural core of various natural products.