Journal Article10.1039/C4CP00346B
Combined activation strain model and energy decomposition analysis methods: a new way to understand pericyclic reactions
93
TL;DR: In this article, the activation strain model (ASM) has been used to quantitatively understand the physical factors that govern the activation barriers of reactions within organic and organometallic chemistry.
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Abstract: The recently introduced activation strain model (ASM) has allowed us to gain more insight into the intimacies of different fundamental processes in chemistry. In combination with the energy decomposition analysis (EDA) method, we have nowadays a very useful tool to quantitatively understand the physical factors that govern the activation barriers of reactions within organic and organometallic chemistry. In this Perspective article, we present selected illustrative examples of the application of this method to pericyclic reactions (Diels–Alder and double group transfer reactions) to show that this methodology nicely complements other more traditional, widely used theoretical methods.
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Citations
The activation strain model and molecular orbital theory.
TL;DR: The activation strain model constitutes a unifying framework that furthers the development of cross‐disciplinary concepts throughout various fields of chemistry and demonstrates how insights into one chemical phenomenon can lead to an improved understanding of another, seemingly completely different chemical process.
325
Theoretical elucidation of the origins of substituent and strain effects on the rates of Diels-Alder reactions of 1,2,4,5-tetrazines.
TL;DR: It is found that the energies to distort alkenes into the Diels-Alder transition-state geometries are smaller than for alkynes in these reactions, and the strained dienophiles, trans-cyclooctene and cyclooctyne, are much more reactive than unstrained trans-2-butene and 2-butyne, because they are predistorted toward the Dieled transition structures.
162
Understanding the reactivity of polycyclic aromatic hydrocarbons and related compounds.
TL;DR: Issues such as the influence of the size and curvature of the system on the reactivity are covered herein, which is crucial for the rational design of novel compounds with tuneable applications in different fields such as materials science or medicinal chemistry.
75
Mechanism and Selectivity of N-Triflylphosphoramide Catalyzed (3+ + 2) Cycloaddition between Hydrazones and Alkenes
Xin Hong,Hatice Başpınar Küçük,Modhu Sudan Maji,Yun-Fang Yang,Magnus Rueping,Kendall N. Houk +5 more
TL;DR: The origins of enantioselectivities when a chiral N-triflylphosphoramide catalyst is employed are explained and the experimental studies that extend the substrate scope of alkenes to ethyl vinyl ethers and thioethers are reported.
75
Aromaticity: Molecular orbital picture of an intuitive concept
Simon C. A. H. Pierrefixe,F. Matthias Bickelhaupt +1 more
- 19 Aug 2007
TL;DR: A molecular-orbital (MO) model of aromaticity is presented that shows that the propensity of the pi electrons is always, that is, in both the aromatic and antiaromatic molecules, to localize the double bonds, against the delocalizing force of the sigma electrons.
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