Triazole-modified Ru-carbene complexes: A valid olefin metathesis pre-catalyst for dynamic covalent chemistry via C=C bond formation
Triazole-modified Ru-carbene complexes: A valid olefin metathesis pre-catalyst for dynamic covalent chemistry via C=C bond formation
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三唑修饰的 Ru-卡宾配合物：通过 C=C 键形成进行动态共价化学的有效烯烃复分解预催化剂
DOI：
10.1016/j.checat.2023.100678
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Shi, Xiaodong
中科院分区：
文献类型：
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作者：
Wang, Chenhuan;Zhang, Shuyao;Yuan, Teng;Jimoh, Abiola Azee;Abreu, Maxwell;Shan, Chuan;Wojtas, Lukasz;Xing, Yangyang;Hong, Xin;Shi, Xiaodong
三唑-钌卡宾络合物 (TA-Rus) 首次被报道为一类新型改性格拉布催化剂，可在较高温度下实现具有挑战性的烯烃复分解，而无需催化剂分解。先前报道的N-束缚Ru-卡宾配合物都遭受快速顺式/反式异构化，导致催化剂反应性显着降低。这些新型 TA-Ru 配合物即使在 80°C 下也能保持活性反式二氯构象，从而能够对具有挑战性的底物进行有效的烯烃复分解。利用这种新型 TA-Ru 催化剂，实现了交叉复分解 (CM)、闭环复分解 (RCM) 和动态共价化学 (DCvC)。令人兴奋的是，TA-Ru 的反应活性优于所有先前报道的 N 配位 Ru-卡宾预催化剂、Grubbs II 和 Hoveyda-Grubbs，使 TA-Rus 成为烯烃催化领域的变革性催化体系。
Triazole-ruthenium carbene complexes (TA-Rus) were reported for the first time as a new class of modified Grubbs catalysts to achieve challenging olefin metathesis at higher temperatures without catalyst decomposition. Previously reported N-tethered Ru-carbene complexes all suffered from rapidcis-/trans-isomerization, causing significantly reduced catalyst reactivity. These new TA-Ru complexes hold the activetrans-dichloro conformation even at 80°C, allowing effective olefin metathesis for challenging substrates. With this new TA-Ru catalyst, cross-metathesis (CM), ring-closing metathesis (RCM), and dynamic covalent chemistry (DCvC) were achieved. Excitingly, the reactivity of TA-Ru prevails all previously reported N-coordinated Ru-carbene pre-catalysts, Grubbs II, and Hoveyda-Grubbs, making TA-Rus a transformative catalytic system in olefin catalysis.