Premium
Computational Study of the Substitution Effect on the Mechanism for the Aza‐ and Arsa‐Wittig Reactions
Author(s) -
Liao HsinYi
Publication year - 2011
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.201190100
Subject(s) - chemistry , wittig reaction , kinetic energy , singlet state , density functional theory , computational chemistry , medicinal chemistry , physics , quantum mechanics , nuclear physics , excited state
The aza‐ and arsa‐Wittig reactions HM=PH 3 + O=CHX → HM=CHX + O=PH 3 (M = N, As; X = H, F, Cl, Me, OMe, NMe 2 , CMe 3 ) were examined using the density functional theory calculations. All of the structures were completely optimized at the B3LYP/6‐311++G** level of theory. The main finding of this work is that the difference between singlet‐triplet splitting of O=CHX and HM=PH 3 play an important role in determining the kinetic and thermodynamic stability of the aza‐ and arsa‐Wittig reactions. When HM=PH 3 with more ylidic character is utilized, the reaction has a smaller activation energy and a larger exothermicity.