A reactive bond orbital investigation of the Diels-Alder reaction between 1,3-butadiene and ethylene: Energy decomposition, state correlation diagram, and electron density analyses

2008 ◽  
Vol 29 (9) ◽  
pp. 1399-1407 ◽  
Author(s):  
Hajime Hirao
Keyword(s):  
Electron Density ◽  
Alder Reaction ◽  
Diels Alder ◽  
Correlation Diagram ◽  
Energy Decomposition ◽  
State Correlation ◽  
Diels Alder Reaction

scholarly journals Heterogeneous Intramolecular Electric Field as a Descriptor of Diels-Alder Reactivity

2020 ◽  
Author(s):  
Matthew Hennefarth ◽  
Anastassia N. Alexandrova
Keyword(s):  
Electric Field ◽  
Electron Density ◽  
Electric Fields ◽  
Alder Reaction ◽  
Diels Alder ◽  
Charge Movement ◽  
External Electric Fields ◽  
Topological Features ◽  
Diels Alder Reaction ◽  
Kinetics Of

<div> <div> <div> <p>External electric fields have proven to be an effective tool in catalysis, on par with pressure and temperature, affecting the thermodynamics and kinetics of a reaction. However, fields in molecules are complicated heterogeneous vector objects, and there is no universal recipe for grasping the exact features of these fields that implicate reactivity. Herein, we demonstrate that topological features of the heterogeneous electric field within the reactant state, as well as of the quantum mechanical electron density – a scalar reporter on the field experienced by the system – can be identified as rigorous descriptors of the reactivity to follow. We scrutinize specifically the Diels-Alder reaction. Its 3-D nature and the lack of a singular directionality of charge movement upon barrier crossing makes the effect of the electric field not obvious. We show that the electric field topology around the dienophile double bond, and the associated changes in the topology of the electron density in this bond are predictors of the reaction barrier. They are also the metrics by which to rationalize and predict how the external field would inhibit or enhance the reaction. The findings pave the way toward designing external fields for catalysis, as well as reading the reactivity without an explicit mechanistic interrogation, for a variety of reactions. </p> </div> </div> </div>

scholarly journals Machine Learning to Predict Diels–Alder Reaction Barriers from the Reactant State Electron Density

2021 ◽  
Vol 17 (10) ◽  
pp. 6203-6213
Author(s):  
Santiago Vargas ◽  
Matthew R. Hennefarth ◽  
Zhihao Liu ◽  
Anastassia N. Alexandrova
Keyword(s):  
Machine Learning ◽  
Electron Density ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction ◽  
State Electron ◽  
Reaction Barriers

Theoretical exammation of the Diels–Alder reaction of 1,3-butadiene with cyclopentadiene and 2H-phosphole

1996 ◽  
Vol 74 (6) ◽  
pp. 839-850 ◽  
Author(s):  
Steven M. Bachrach ◽  
Laureta M. Perriott
Keyword(s):  
Electron Density ◽  
Alder Reaction ◽  
Diels Alder ◽  
Trans Conformation ◽  
Remarkable Similarity ◽  
Diels Alder Reaction ◽  
Two Systems ◽  
Density Analysis ◽  
Electron Density Analysis

All Diels–Alder reactions between 1,3-butadiene and cyclopentadiene or 2H-phosphole have been examined at the MP4SDQ/6-31G*//HF/6-31G* level. There is remarkable similarity between the two systems. The thermodynamic product is the bicyclo[4.2.0]nonadiene while the kinetic product is the norbornene product. There is a slight kinetic preference for the endo addition and for the butadiene to be in the s-trans conformation. Except for the case where butadiene is the diene component and addition is endo, the reactions are concerted and synchronous. In these other two cases, the reaction is stepwise with a diradical intermediate.Key words: phosphole, Diels–Alder reaction, topological electron density analysis.

scholarly journals The effect of electron density in furan pendant group on thermal-reversible Diels–Alder reaction based self-healing properties of polymethacrylate derivatives

RSC Advances ◽  
2018 ◽  
Vol 8 (69) ◽  
pp. 39432-39443 ◽  
Author(s):  
Keum-Seob Byun ◽  
Won Jae Choi ◽  
Ha-Young Lee ◽  
Min-Ji Sim ◽  
Sang-Ho Cha ◽  
...  
Keyword(s):  
Electron Density ◽  
Alder Reaction ◽  
Diels Alder ◽  
Pendant Group ◽  
Self Healing ◽  
Diels Alder Reaction ◽  
Healing Efficiency

Herein, we discuss the effect of electron density in a furan pendant group on the thermally reversible Diels–Alder (DA) reaction based self-healing efficiency in polymethacrylate derivatives.

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