Photocatalytic Site‐Selective Cascade Radical Addition of Biaryl Ynones for the Construction of Spiro‐ and Fused Carbon Rings

• Published in: Chinese journal of chemistry Vol. 42; no. 14; pp. 1599 - 1605
• Main Authors: Liu, Kairui, Zhao, Chunhang, Gu, Liji, Li, Xiang, Yan, Jiali, Lao, Siqi, Huan, Weiwei, Zhang, Yan
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY‐VCH Verlag GmbH & Co. KGaA 13.03.2024; Wiley Subscription Services, Inc
• Subjects: Alkoxycarbonyl radical; Biaryls; Carbon cycle; Cascade cyclization; Chemical reactions; Coupling (molecular); Cyclic compounds; Dearomatization; Free radicals; Functional groups; Photocatalysis; Radical reactions; Regioselectivity; Ynones
• ISSN: 1001-604X; 1614-7065
• DOI: 10.1002/cjoc.202400149

Comprehensive Summary Functionalized free radical addition/cyclization reactions represent an efficient way for introducing new functionality or coupling fragments to molecules. Ynones are good regional selectivity radical acceptors in organic synthesis, and many of bio‐relevant cyclic compounds could be easily obtained by direct radical cyclization reaction. Here, we report a photocatalytic cascade radical addition of biaryl ynones, for the divergent synthesis of privileged carbon cycles. Additionally, further transformation of the multi‐functional group product into a variety of other derivatives demonstrates the synthetic value of this developed method. It is worth noting that this is the first example of alkoxycarbonyl radical addition to ynones, providing a series of novel functional derivatives. An IrIII‐catalyzed cascade radical addition reaction of biaryl ynones to access two classes of carbon rings has been developed. Key to the desired transformations is the regioselective radical addition to different substituted alkyne.