Asymmetric Ruthenium-Catalyzed C-H Activation by a Versatile Chiral-Amide-Directing Strategy.

ABSTRACT

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).