Advances on Quasi-classical Molecular Dynamics of Organic Reaction Mechanisms

Zhang, Kairui; Wang, Yaya; Zhu, Hongdan; Peng, Qian

doi:10.6023/cjoc202102036

Cited by 3 publications

(2 citation statements)

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“…Pyrrole and Ket3 then form a cation−π complex IN1 , which undergoes electrophilic addition via TS2 , with a quite low activation free energy, 2.8 kcal/mol. Our calculations found that the addition transition state TS2 is ambimodal, , where two intermediates, IN2 and IN3 , can be generated. Scanning the C2–C11 and C3–C11 bond distances showed that TS2 bifurcates to two potential wells of IN2 and IN3 (Figure A).…”

Section: Resultsmentioning

confidence: 76%

“…There are three patterns of reaction selectivity control, namely, kinetic, thermodynamic, and dynamic controls. , Knowing the exact pattern of selectivity control is important and helpful to understanding these reactions and to designing new reactions in the future. Usually, a reaction’s selectivity is controlled by one of these three patterns.…”

Section: Introductionmentioning

confidence: 99%

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Dynamically or Kinetically Controlled? Computational Study of the Mechanisms of Electrophilic Aminoalkenylation of Heteroaromatics with Keteniminium Ions

Zhang,

2024

J. Org. Chem.

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Quantum chemical calculations and molecular dynamics simulations were applied to study the electrophilic aminoalkenylation of heteroaromatics with keniminium ions. Post-transition state bifurcation (PTSB) was found in the electrophilic addition step for the aminoalkenylation of pyrroles and indoles, and the selectivity for these reactions was dynamically controlled. However, the aminoalkenylation of furan was kinetically controlled because no apparent PTSB was found in the electrophilic addition step. The substituents on the keteniminium ions can also affect the dynamic results for the aminoalkenylations to pyrroles: the C2-aminoalkenylated product is much more favored over the C3-aminoalkenylated product for keteniminium ions with electron-donating substituents, while the product ratio (C2 product/C3 product) decreased when stronger electron-withdrawing substituents were applied.

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Section: Resultsmentioning

confidence: 76%

Section: Introductionmentioning

confidence: 99%