Zhang Yongqiang, Fu Dongmin, Chen Ziyang, Cui Rongqi, He Wenlong, Wang Hongyao, Chen Jiajin, Chen Yufei, Li Shi-Jun, Lan Yu, Duan Chunying, Jin Yunhe
State Key Laboratory of Fine Chemicals, School of Chemistry, Dalian University of Technology, Dalian, 116024, China.
Green Catalysis Center, College of Chemistry, Zhengzhou University, Zhengzhou, 450001, China.
Nat Commun. 2024 Oct 4;15(1):8619. doi: 10.1038/s41467-024-53021-x.
The challenging synthesis of thermodynamic-unfavored cis-olefins through catalytic cross-coupling reactions requires the synergistic interaction of substrate-activating units and configuration-regulating catalysts. Successfully hitting these two birds with one stone, we herein develop a convenient photoredox access to Z-alkenes from alkynes and light alkanes with a bifunctional iron-catalyzed system possessing both C(sp)-H activation and configuration-controlling abilities. The protocol exhibits 100% atom utilization, mild conditions, a broad substrate scope, and compatibility with multitudinous functional groups. The detailed reaction mechanism and the origin of geometry regulation are well investigated by experimental and computational studies. Progressively, a catalytic amount of diaryl disulfides is introduced for consecutive photoinduced Z-E isomerization via reversible radical addition and flipping. Big steric hindrance substituents assembled on the disulfide emerge necessity for suppressing double-bond migration. This tandem strategy paves a promising way for stereoselective alkene construction and will bring significant inspiration for the development of transition metal photocatalysis.
通过催化交叉偶联反应合成热力学上不利的顺式烯烃具有挑战性，这需要底物活化单元和构型调节催化剂之间的协同相互作用。我们在此成功地一石二鸟，开发了一种方便的光氧化还原方法，利用具有C(sp)-H活化和构型控制能力的双功能铁催化体系，从炔烃和轻质烷烃制备Z-烯烃。该方法具有100%的原子利用率、温和的条件、广泛的底物范围以及与众多官能团的兼容性。通过实验和计算研究对详细的反应机理和几何构型调节的起源进行了深入研究。逐步地，引入催化量的二芳基二硫化物，通过可逆的自由基加成和翻转进行连续的光诱导Z-E异构化。二硫化物上组装的大空间位阻取代基对于抑制双键迁移是必要的。这种串联策略为立体选择性烯烃的构建铺平了一条有前途的道路，并将为过渡金属光催化的发展带来重要的启发。
