Marchois J, Fressigné C, Lecachey B, Maddaluno J
Laboratoire COBRA, CNRS UMR 6014 & FR 3038, Université de Rouen and INSA de Rouen, 76821-Mont St Aignan Cedex, France.
Chem Commun (Camb). 2015 Jun 18;51(48):9801-4. doi: 10.1039/c5cc01549a.
The competition between basicity and nucleophilicity of two standard organolithium reagents was studied using DFT. Comparing the reactivity of solvated (MeLi)2 and (LDA)2 toward propanal finally explains why methyllithium adds onto the carbonyl while LDA deprotonates the α-position, in accord with experiment and Ireland's deprotonation TS.
利用密度泛函理论（DFT）研究了两种标准有机锂试剂的碱性和亲核性之间的竞争关系。比较溶剂化的(MeLi)₂和(LDA)₂对丙醛的反应活性，最终解释了为什么甲基锂加成到羰基上，而LDA使α位去质子化，这与实验结果和爱尔兰去质子化过渡态一致。
