化学
分子内力
双生的
光催化
自由基环化
氢原子萃取
化学选择性
激进的
三键
分子间力
表面改性
功能群
光化学
光催化
组合化学
催化作用
立体化学
双键
有机化学
分子
物理化学
聚合物
作者
Zhongyu Qi,Zhijie Zhang,Yang Li,Di Zhang,Junhao Lu,Jun Wei,Siping Wei,Qiang Fu,Xiaohua Du,Dong Yi
标识
DOI:10.1002/adsc.202100517
摘要
Abstract We report an example of non‐dearomative trifunctionalizing ipso ‐spirocyclization of unactivated alkenes through photoredox‐catalyzed, nitrogen‐radical‐triggered cyclization‐trapping‐translocation‐cyclization cascade, providing a single‐step modular access to spiroaminal frameworks through the sequential formation of one C−C bond and two geminal C−N bonds. The developed protocol utilizes not only internal and terminal olefinic oxime esters, but also olefinic amides as nitrogen radical precursors, and features a broad substrate scope, wide functional group compatibility, easy scalability, and potential for product derivatization and late‐stage functionalization of bioactive estrone derivatives. Importantly, the mechanistic studies including DFT calculations indicate that the photocatalytic trifunctionalizing ipso ‐spirocyclization undergoes a radical relay cascade of intramolecular 5‐ exo ‐ trig cyclization, intermolecular radical trapping, 1,5‐hydrogen atom transfer, and sequential 5‐ endo ‐ trig cyclization, which provides another reaction mode of alkenes. magnified image
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