Phosphine-Catalyzed Allylic Alkylation of (Hetero)Aryl Alkynes with Pronucleophiles: Concise Total Synthesis of (& PLUSMN;)-Esermethole

Allylic alkylations are valuable in the constructionof versatilecarbon-carbon bonds, which are mostly catalyzed by noble transitionmetals with additional waste byproduct generation. Here, we presentthe first organophosphine-catalyzed allylic alkylation of (hetero)arylalkynes with various carbo-nucleophiles. The methodology is highlyatom economical and compatible with a wide substrate scope (more than38 examples). Moreover, the reaction could be easily scaled up, anddeuterium labeling experiments have been conducted to elucidate theplausible mechanism. Finally, the protocol has been utilized to achievethe concise total synthesis of natural product (& PLUSMN;)-esermethole.

Automated summary

In this study, the first organophosphine-catalyzed allylic alkylation of (hetero)arylalkynes with various carbo-nucleophiles is described. The method is highly atom economical and compatible with a wide range of substrates, leading to the concise total synthesis of natural product (& PLUSMN;)-esermethole.