Affiliation:
1. Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs School of Chemistry and Chemical Engineering Frontiers Science Center for Transformative Molecules Shanghai Jiao Tong University Shanghai 200240 China
Abstract
AbstractHerein, we report a photoinduced approach for hydroarylation of unactivated olefins using 4‐hydroxycoumarins as the arylating reagent. Key to the success of this reaction is the conversion of nucleophilic 4‐hydroxycoumarins into electrophilic carbon radicals via photocatalytic arene oxidation, which not only circumvents the polarity‐mismatch issue encountered under ionic conditions but also accommodates a broad substrate scope and inhibits side reactions that were previously observed. Moreover, divergent reactivity was achieved by changing the photocatalyst, enabling a subsequent [2+2] cycloaddition to deliver cyclobutane‐fused pentacyclic products that are otherwise challenging to access in high yields and with high diastereoselectivity. Mechanistic studies have elucidated the mechanism of the reactions and the origin of the divergent reactivity.
Funder
National Natural Science Foundation of China
Shanghai Jiao Tong University