Azaborine benzylic ion stability and reactivity in ionic polymerization
Azaborine benzylic ion stability and reactivity in ionic polymerization
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离子聚合中氮杂硼啉苄基离子的稳定性和反应活性
DOI：
10.1039/d1ob02467a
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发表时间：
2022
影响因子：
3.2
通讯作者：
Klausen, Rebekka S.
中科院分区：
文献类型：
--
作者：
Wakefield IV, Herbert;Jiang, Qifeng;Klausen, Rebekka S.
苯甲基阳离子和阴离子与关键有机转化机制有关，如苯乙烯聚合。研究了BN取代CC键对苄基离子反应活性的影响以及BN 2-乙烯基萘（BN 2 VN）离子聚合的影响。计算表明，接近的N供体的阳离子的影响BN苄基阳离子的稳定性，合理化不成功的质子化BN 2 VN。有机锂试剂通过假设的缔合机理与BN 2 VN和相关BN萘进行干净的亲核芳族取代。这些结果表明主族芳香取代的设计原则。
Benzylic cations and anions are implicated in the mechanism of critical organic transformations, such as styrene polymerization. We investigate the influence of BN for CC bond substitution on the reactivity of benzylic ions and the effect on BN 2-vinylnaphthalene (BN2VN) ionic polymerization. Calculations suggest that the proximity of a N donor to a cation influences the stability of a BN benzylic cation, rationalizing unsuccessful protonation of BN2VN. Organolithium reagents undergo clean nucleophilic aromatic substitution with BN2VN and related BN naphthalenes via a hypothesized associative mechanism. These results suggest design principles for main group aromatic substitution.