Duan Yurong, Zhang Kai, Xing Tongtong, Bai Yubin, Li Jinfeng, Yang Xiaojun, Zhao Yu, Zhang Qiuyu
Shaanxi Key Laboratory of Chemical Reaction Engineering, College of Chemistry and Chemical Engineering, Yan'an University, Yan'an, Shaanxi 716000, China.
Jiangsu Key Lab of Green Synthetic Chemistry for Functional Materials, School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu 221116, China.
Chem Commun (Camb). 2024 Aug 29;60(71):9582-9585. doi: 10.1039/d4cc01619j.
A metal-free photoinduced alkynylation of carbamoyl radicals with hypervalent iodine(III) reagents for a facile synthesis of alkynyl amides is described. This protocol features good functional group tolerance and a broad substrate scope for direct synthesis of alkynyl amide derivatives in good to excellent yields under mild and redox-neutral reaction conditions. The synthetic application is demonstrated by the late-stage installation of alkynyl amides into natural products and active pharmaceutical relevant molecules. The mechanistic studies indicated the simultaneous existence of photoredox catalytic and direct photoexcited processes, and the quantum yields confirmed the occurrence of the radical chain propagation process.
本文描述了一种无金属光诱导的氨基甲酰基自由基与高价碘（III）试剂的炔基化反应，用于炔基酰胺的简便合成。该方法具有良好的官能团耐受性和广泛的底物范围，可在温和且氧化还原中性的反应条件下直接合成炔基酰胺衍生物，产率良好至优异。通过将炔基酰胺后期引入天然产物和活性药物相关分子中，证明了其合成应用。机理研究表明，光氧化还原催化和直接光激发过程同时存在，量子产率证实了自由基链传播过程的发生。
