Investigation of the Markovnikov Regioselectivity Rule in terms of ABEEM-σπ Model: A Site Activation Method

Insight into generalized local softness based on ABEEM‐σπ method: Electrophilic additions to alkenes

“…It is consistent with the ab initio and previous studies. [24,28,41,44] This indicates that the ABEEM-σπ model could well describe the regioselectivity rule in terms of the local HSAB principle. In order to investigate the chemical reactivity of the alkenes, the correlations between the differences in the activation energies of the Markovnikov and anti-Markovnikov additions and Δss or ΔSS G of the Markovnikov and anti-Markovnikov additions have been studied, and correlation pictures are shown in Figures 3 and 4.…”

“…In this paper, electrophilic additions of H 2 O, HF, HCl, and HBr to a series of the asymmetric alkenes with substituents CH 3 , CH 2 CH 3 , (CH 3 ) 2 , OH, OCH 3 , COOH, CN, COF, CHO and OCN (totally 40 reactions), have been revisited from a viewpoint of softness based on the ABEEM-σπ method. The geometrical structures refer to our previous studies [28] and Data S1 (Table S1 and Table S2), the activation energies have been calculated at CCSD(T)//aug-cc-PVTZ//MP2/6-311++G(3df,3pd) level of theory, and given in Table 1. In addition, the activation energies have been calculated at MP2/6-311++G(3df,3pd) level of theory, and given in Table S3.…”

“…Therefore, how to deal with a double bond in the model is very important. In view of this, Yang and co-workers proposed and developed the atombond electronegativity equalization method plus σπ (ABEEM-σπ) model [22][23][24][25][26][27][28][29] based on the DFT. [30,31] One of the significant characteristics of the ABEEMσπ method is that the double bond is explicitly partitioned, and a molecule is decomposed into atomic regions, chemical bond regions, that is, σ and π bond regions, and lone-pair regions.…”

“…The addition reaction to the alkenes [24,28,[32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48] is one of the most widely studied objects, and it is an important method used in many industrial productions. Schematic competing electrophilic routes to alkenes are depicted in Scheme 1.…”

“…[24] Studies show that the ABEEM-σπ method can give a reasonable explanation of the reaction mechanism from multiple perspectives. [24,28] In this work, electrophilic additions of H 2 O, HF, HCl, and HBr to a series of asymmetric alkenes were investigated by means of ab initio and ABEEM-σπ method. The main purpose of this article is to understand the significance of the generalized local softness in studying the chemical reactivity.…”