Photocatalytic, modular difunctionalization of alkenes enabled by ligand-to-metal charge transfer and radical ligand transfer.
Photocatalytic, modular difunctionalization of alkenes enabled by ligand-to-metal charge transfer and radical ligand transfer.
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DOI：
10.1039/d3sc05231a
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发表时间：
2023-12-20
期刊：
影响因子：
8.4
通讯作者：
West, Julian G.
中科院分区：
文献类型：
--
作者：
Bian, Kang-Jie;Nemoto Jr, David;Chen, Xiao-Wei;Kao, Shih-Chieh;Hooson, James;West, Julian G.
配体到金属的电荷转移(LMCT)是一种机械性的策略，它为利用地球上丰富的元素获得各种开壳物种提供了强有力的工具，并在最近几年有了巨大的增长。然而，在由LMCT反应性驱动的许多反应流形中，烯烃模块去功能化的通用和催化方案仍然未知。利用铁催化的配体-金属电荷转移和自由基转移(RLT)的协同作用，我们报道了一种光催化的模块化烯烃双官能化反应，使用廉价的铁盐作为自由基的引发剂和终止剂。此外，战略性地使用氟原子转移试剂允许烯烃的一般氟氯化，提供了第一个利用稀土元素光催化形成卤间化合物的例子。本研究证明了正交亲核试剂(TM N3和NaC l)直接转化为相应的开壳自由基物种的范围广、条件温和、通用性强，为催化获得邻位二叠氮化物和同/杂二卤化物基元提供了一种可靠的手段。这些官能团是医药和材料化学中重要的前体/中间体。初步的机理研究支持这些转化的自由基性质，揭示了串联LMCT/RLT作为催化烯烃双官能化的强大反应歧管。简单铁盐通过配体-金属电荷转移(LMCT)和自由基转移(RLT)或氟原子转移(FAT)的合并，能够光催化烯烃的重氮化、二氯化和氟氯化。
Ligand-to-metal charge transfer (LMCT) is a mechanistic strategy that provides a powerful tool to access diverse open-shell species using earth abundant elements and has seen tremendous growth in recent years. However, among many reaction manifolds driven by LMCT reactivity, a general and catalytic protocol for modular difunctionalization of alkenes remains unknown. Leveraging the synergistic cooperation of iron-catalyzed ligand-to-metal charge transfer and radical ligand transfer (RLT), here we report a photocatalytic, modular difunctionalization of alkenes using inexpensive iron salts catalytically to function as both radical initiator and terminator. Additionally, strategic use of a fluorine atom transfer reagent allows for general fluorochlorination of alkenes, providing the first example of interhalogen compound formation using earth abundant element photocatalysis. Broad scope, mild conditions and versatility in converting orthogonal nucleophiles (TMSN3 and NaCl) directly into corresponding open-shell radical species are demonstrated in this study, providing a robust means towards accessing vicinal diazides and homo-/hetero-dihalides motifs catalytically. These functionalities are important precursors/intermediates in medicinal and material chemistry. Preliminary mechanistic studies support the radical nature of these transformations, disclosing the tandem LMCT/RLT as a powerful reaction manifold in catalytic olefin difunctionalization. Simple iron salts are able to photocatalyze the diazidation, dichlorination, and fluorochlorination of alkenes via the merger of ligand-to-metal charge transfer (LMCT) and either radical ligand transfer (RLT) or fluorine atom transfer (FAT).
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影响因子：
3.3
作者：
Isse, Abdirisak A.;Lin, Ching Yeh;Gennaro, Armando
通讯作者：
Gennaro, Armando
影响因子：
16.6
作者：
Bian, Kang-Jie;Kao, Shih-Chieh;Nemoto, David, Jr.;Chen, Xiao-Wei;West, Julian G.
通讯作者：
West, Julian G.
影响因子：
5.2
作者：
Liu, Wei;Wu, Qiang;Hu, Peng
通讯作者：
Hu, Peng
影响因子：
21.8
作者：
Cresswell AJ;Eey ST;Denmark SE
通讯作者：
Denmark SE
通过可见光光催化进行烯烃双官能化
影响因子：
1.8
作者：
Cao, Min-Yi;Ren, Xiang;Lu, Zhan
通讯作者：
Lu, Zhan