Competing 1,n-elimination reactions of 1-Bromo-5-bromomethyl-6,6-dichlorobicyclo[3.1.0]hexane: A strained 1,3-bridged cyclopropene and a vinylcarbene as reactive intermediates

Tetrahedron ◽  
1996 ◽  
Vol 52 (47) ◽  
pp. 14641-14650 ◽  
Author(s):  
Jürgen Weber ◽  
Udo H. Brinker
Keyword(s):  
Reactive Intermediates ◽  
Elimination Reactions

Radical Enzymes Control the Chemistry of Their Highly Reactive Intermediates Using the Quantum Coulombic Effect

2020 ◽  
Author(s):  
Hossein Khalilian ◽  
Gino A. DiLabio
Keyword(s):  
Hydrogen Bonding ◽  
Molecular Orbital ◽  
Reactive Intermediates ◽  
Hydrogen Bonding Interaction ◽  
Orbital Ordering ◽  
Dynamic Nature ◽  
Radical Intermediate ◽  
Highest Occupied Molecular Orbital ◽  
Bonding Interaction ◽  
Close Proximity

Here, we report an exquisite strategy that the B12 enzymes exploit to manipulate the reactivity of their radical intermediate (Adenosyl radical). Based on the quantum-mechanic calculations, these enzymes utilize a little known long-ranged through space quantum Coulombic effect (QCE). The QCE causes the radical to acquire an electronic structure that contradicts the Aufbau Principle: The singly-occupied molecular orbital (SOMO) is no longer the highest-occupied molecular orbital (HOMO) and the radical is unable to react with neighbouring substrates. The dynamic nature of the enzyme and its structure is expected to be such that the reactivity of the radical is not restored until it is moved into close proximity of the target substrate. We found that the hydrogen bonding interaction between the nearby conserved glutamate residue and the ribose ring of Adenosyl radical plays a crucial role in manipulating the orbital ordering

Radical Enzymes Control the Chemistry of Their Highly Reactive Intermediates Using the Quantum Coulombic Effect

2020 ◽  
Author(s):  
Hossein Khalilian ◽  
Gino A. DiLabio
Keyword(s):  
Hydrogen Bonding ◽  
Molecular Orbital ◽  
Reactive Intermediates ◽  
Hydrogen Bonding Interaction ◽  
Orbital Ordering ◽  
Dynamic Nature ◽  
Radical Intermediate ◽  
Highest Occupied Molecular Orbital ◽  
Bonding Interaction ◽  
Close Proximity

Here, we report an exquisite strategy that the B12 enzymes exploit to manipulate the reactivity of their radical intermediate (Adenosyl radical). Based on the quantum-mechanic calculations, these enzymes utilize a little known long-ranged through space quantum Coulombic effect (QCE). The QCE causes the radical to acquire an electronic structure that contradicts the Aufbau Principle: The singly-occupied molecular orbital (SOMO) is no longer the highest-occupied molecular orbital (HOMO) and the radical is unable to react with neighbouring substrates. The dynamic nature of the enzyme and its structure is expected to be such that the reactivity of the radical is not restored until it is moved into close proximity of the target substrate. We found that the hydrogen bonding interaction between the nearby conserved glutamate residue and the ribose ring of Adenosyl radical plays a crucial role in manipulating the orbital ordering

Survey for Transition of Normal Reaction

2018 ◽  
Vol 5 (3) ◽  
Author(s):  
Hassan Akbari Rahimi
Keyword(s):  
Transition State ◽  
Reactive Intermediates ◽  
The State ◽  
Energy Profile ◽  
Normal Reaction ◽  
Unstable Molecules ◽  
The Difference ◽  
Bond Vibration ◽  
Unstable Molecule ◽  
Profile Diagram

Transition of reaction is a short-lived unstable molecule in a reaction which is formed in between the reaction when reactants change into products. Whereas, transition state is just the state before formation of new molecule (involves breaking of bonds of reactants and formation of new ones) Transition of reaction differs from a transition state in that the intermediate has a discrete lifetime (be it a few nanoseconds or many days), whereas a transition state lasts for just one bond vibration cycle. Intermediates may be unstable molecules (in which case they are called reactive intermediates) or highly stable molecules. The difference between them can be better described through the energy profile diagram.

Solvolytic reactions of empiric 3-methanesulfonyloxy-7-benzoyloxy-5β,6β-cyclopropanocholestanes

1986 ◽  
Vol 51 (2) ◽  
pp. 436-446 ◽  
Author(s):  
Ladislav Kohout ◽  
Vijay Kumar Sethi ◽  
Jaroslav Zajíček ◽  
Alexander Kasal
Keyword(s):  
Spectral Methods ◽  
Elimination Reactions

Acetolysis of 3-methanesulfonyloxy-7-benzoyloxy-5β,6β-cyclopropanocholestanes with various configurations in positions 3 and 7 is described and the products are assigned structure using spectral methods. The 7-substituted compounds show greater propensity to elimination reactions than the 7-unsubstituted ones.

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