Copper-Catalyzed Remote Asymmetric Yne-Allylic Substitution of Yne-Allylic Esters with Anthrones

Abstract

Anthrones are key structural motifs in many natural products and pharmaceutical chemicals. However, due to its unique tricyclic aromatic structure, the synthetic space for the development of chiral anthrone derivatives is largely limited. By utilizing the potential of the copper-catalyzed remote asymmetric yne-allylic substitution reaction, we describe the first example of coppercatalyzed highly regio-and enantioselective remote yne-allylic substitution on various yne-allylic esters with anthrones under a mild reaction condition, which afforded a range of enantioenriched 1,3-enynes with exhibiting broad functional group tolerance across 51 examples.

Copper-Catalyzed Dual Remote Asymmetric Vinylogous Alkynylallylic Substitution of Yne-Allylic Esters with Coumarins

“…Recently, a new copper–vinylvinylidene complex was reported by Fang et al, He et al, Xu et al, our group, and other groups, which formed from the substrate that when an extended CC bond or aryl group assembly into propargylic alcohol derivatives (Scheme a). In particular, the He group described an elegant copper-catalyzed enantioselective propargylic amination of yne-allylic esters with amines at the γ position of the copper–vinylvinylidene complex to yield chiral 1,4-enyne products. , Xu et al and our group independently reported the copper-catalyzed remote asymmetric alkynylallylic substitution of yne-allylic esters with 1,3-dicarbonyl compounds or sodium sulfinates at the ε position of the copper–vinylvinylidene complex. In addition, both the He and Xu groups independently reported the remote copper-catalyzed asymmetric substitution of yne-thiophene esters.…”