Asymmetric Ruthenium‐Catalyzed C−H Activation by a Versatile Chiral‐Amide‐Directing Strategy

A versatile and readily available chiral amide directing group has been developed for the ruthenium(II)‐catalyzed asymmetric C−H activation. Asymmetric C−H activation of the related chiral benzamides with various olefins, aldehydes and propargylic alcohols has been accomplished with high stereoselectivities, affording a series of chiral products including 3,4‐dihydroisocoumarins (up to 96% ee), isocoumarins (up to 92% ee), phthalides (up to 99% ee), chiral bicyclo[2.2.1]heptanes (>20:1 dr), 4‐alkylidene‐3,4‐dihydroisocoumarins (up to 97% ee) and allenes (>20:1 dr). Importantly, our methodologies enabled concise syntheses of many biologically active compounds and natural products (e.g., Montroumarin, Cyclosporone E, Cyclosporone Q, Concentricolide, Chuangxinol, and Eleutherol).