Highly Stereoselective Assembly of Polycyclic Molecules from 1,6-Enynes Triggered by Rhodium(III)-Catalyzed C-H Activation

An Rh(III)-catalyzed C-H activation of pyrazolones with 1,6-enynes was investigated. The regioselectivity of the C-H activation/alkyne insertion is readily solved by using symmetric enyne coupling partners, and a C-H activation-triggered cascade reaction is realized, which involves alkyne insertion, tautomerization, and double cyclization to offer a class of structurally complex polycyclic architectures. This cascade reaction tolerates a broad substrate scope in high regioselectivity and stereospecificity and furnishes three new chemical bonds and four chiral centers in a single operation. Various derivatizations of the polycyclic scaffolds are conducted, providing products with ample space for further functional transformations.