Modular preparation of cationic bipyridines and azaarenes via C-H activation.
Modular preparation of cationic bipyridines and azaarenes via C-H activation.
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DOI：
10.1039/d3sc04864k
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发表时间：
2023-11-29
期刊：
影响因子：
8.4
通讯作者：
Yang, Jenny Y.
中科院分区：
文献类型：
--
作者：
King, Ryan P.;Yang, Jenny Y.
联吡啶由于其氧化还原和光化学性质以及作为过渡金属配体的实用性而在有机和无机化学中普遍存在。联吡啶和氮杂芳烃上的阳离子取代基作为强吸电子官能团是有价值的，其也增强了在极性溶剂中的溶解度，但是没有用于直接官能化的通用方法。本发明公开了一种制备三甲基铵和三芳基膦取代的联吡啶和氮杂杂环的通用方法。这种方法展示了吡啶N-氧化物的C-H活化，其使得能够高度模块化和可扩展地合成各种各样的阳离子带电氮杂芳烃。在联吡啶衍生物上添加三甲基铵官能团导致更多的阳极还原电位（高达700 mV）和增加的电化学可逆性相比，中性未官能化的联吡啶。此外，4-三苯基膦化的联喹啉，使相应的Re（CO）3Cl络合物的金属化导致还原电位400 mV以上的中性衍生物的阳极。本发明公开了一种制备三甲基铵和三芳基膦取代的联吡啶和氮杂杂环的通用方法。的阳离子官能团的影响进行了电化学研究。
Bipyridines are ubiquitous in organic and inorganic chemistry because of their redox and photochemical properties and their utility as ligands to transition metals. Cationic substituents on bipyridines and azaarenes are valuable as powerful electron-withdrawing functionalities that also enhance solubility in polar solvents, but there are no general methods for direct functionalization. A versatile method for the preparation of trimethylammonium- and triarylphosphonium-substituted bipyridines and azaheterocycles is disclosed. This methodology showcases a C–H activation of pyridine N-oxides that enables a highly modular and scalable synthesis of a diverse array of cationically charged azaarenes. The addition of trimethylammonium functionalities on bipyridine derivatives resulted in more anodic reduction potentials (up to 700 mV) and increased electrochemical reversibility compared to the neutral unfunctionalized bipyridine. Additonally, metallation of 4-triphenylphosphinated biquinoline to make the corresponding Re(CO)3Cl complex resulted in reduction potentials 400 mV more anodic than the neutral derivative. A versatile method for the preparation of trimethylammonium- and triarylphosphonium-substituted bipyridines and azaheterocycles is disclosed. The impact of the cationic functionalities was investigated electrochemically.
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DOI：
10.1002/anie.201702107
发表时间：
2017-05-15
期刊：
Angewandte Chemie (International ed. in English)
影响因子：
--
作者：
Avila CM;Patel JS;Reddi Y;Saito M;Nelson HM;Shunatona HP;Sigman MS;Sunoj RB;Toste FD
通讯作者：
Toste FD
影响因子：
16.6
作者：
Brak, Katrien;Jacobsen, Eric N.
通讯作者：
Jacobsen, Eric N.
关于伪二聚体番茄红素生物碱的合成研究：ComplanadineB的总合成。
影响因子：
16.6
作者：
Newton, James N.;Fischer, Daniel F.;Sarpong, Richmond
通讯作者：
Sarpong, Richmond
影响因子：
7.3
作者：
Olberg, Dag E.;Arukwe, Joseph M.;Cuthbertson, Alan
通讯作者：
Cuthbertson, Alan
影响因子：
5.2
作者：
Bugaenko, Dmitry, I;Yurovskaya, Marina A.;Karchava, Alexander, V
通讯作者：
Karchava, Alexander, V