Methyl Cation Affinities of Canonical Organic Functional Groups
Methyl Cation Affinities of Canonical Organic Functional Groups
复制标题
DOI：
10.1021/acs.joc.0c02327
复制
发表时间：
2021-02-17
影响因子：
3.6
通讯作者：
Van Vranken, David L.
中科院分区：
文献类型：
--
作者：
Kadish, Dora;Mood, Aaron D.;Van Vranken, David L.
计算有机化学中典型亲核官能团的甲基阳离子亲和力。这些甲基阳离子亲和力通过溶剂化模型 (MCA*) 计算得出，当它们缩放至 Mayr 参考阳离子 (4-MeOC6H4)(2)CH+ (Mayr E = 0) 时，可在非质子条件下与 Mayr 方程中的 Ns(N) 项建立经验相关性。发现高反应性阴离子亲核试剂给出了单独的相关性，而一些叶立德和磷化合物被确定给出了较差的相关性。 MCA* 是针对代表有机化学中典型官能团的各种简单分子进行估计的。基于线性相关性，我们估计有机官能团的亲核性范围（从 C-C 键到假设的叔丁基碳负离子）与参考亲电子试剂的亲核性范围约为 50 个数量级。
Methyl cation affinities are calculated for the canonical nucleophilic functional groups in organic chemistry. These methyl cation affinities, calculated with a solvation model (MCA*), give an emprical correlation with the Ns(N) term from the Mayr equation under aprotic conditions when they are scaled to the Mayr reference cation (4-MeOC6H4)(2)CH+ (Mayr E = 0). Highly reactive anionic nucleophiles were found to give a separate correlation, while some ylides and phosphorus compounds were determined to give a poor correlation. MCA*s are estimated for a broad range of simple molecules representing the canonical functional groups in organic chemistry. On the basis of a linear correlation, we estimate the range of nucleophilicities of organic functional groups, ranging from a C-C bond to a hypothetical tert-butyl carbanion, toward the reference electrophile to be about 50 orders of magnitude.