Department of Chemistry, University of California Irvine, Irvine, California 92697, United States.
Department of Computer Science, University of California Irvine, Irvine, California 92697, United States.
J Org Chem. 2020 Mar 20;85(6):4096-4102. doi: 10.1021/acs.joc.9b03187. Epub 2020 Mar 4.
Calculated methyl anion affinities are known to correlate with experimentally determined Mayr parameters for individual organic functional group classes but not between neutral and cationic organic electrophiles. We demonstrate that methyl anion affinities calculated with a solvation model (MAA*) give a linear correlation with Mayr parameters for a broad range of functional groups. Methyl anion affinities (MAA*), plotted on the log scale of Mayr , provide insights into the full range of electrophilicity of organic functional groups. On the Mayr scale, the electrophilicity toward the methyl anion spans 180 orders of magnitude.
已知计算得到的甲基阴离子亲和力与个别有机官能团类别的实验测定的迈尔参数相关，但与中性和阳离子有机亲电试剂无关。我们证明，用溶剂化模型（MAA*）计算得到的甲基阴离子亲和力与广泛的官能团的迈尔参数呈线性相关。以迈尔的对数标度绘制的甲基阴离子亲和力（MAA*）提供了对有机官能团的全部亲电性范围的深入了解。在迈尔标度上，对甲基阴离子的亲电性跨越 180 个数量级。
