In organic chemistry, an electrocyclic reaction is a type of pericyclic rearrangement where the net result is one pi bond being converted into one sigma bond or vice versa. These reactions are usually categorized by the following criteria:
Reactions can be either photochemical or thermal.
Reactions can be either ring-opening or ring-closing (electrocyclization).
Depending on the type of reaction (photochemical or thermal) and the number of pi electrons, the reaction can happen through either a conrotatory or disrotatory mechanism.
The type of rotation determines whether the cis or trans isomer of the product will be formed.
The Nazarov cyclization reaction is a named electrocyclic reaction converting divinylketones to cyclopentenones.
A classic example is the thermal ring-opening reaction of 3,4-dimethylcyclobutene. The cis isomer exclusively yields whereas the trans isomer gives the trans,trans diene:
This reaction course can be explained in a simple analysis through the frontier-orbital method: the sigma bond in the reactant will open in such a way that the resulting p-orbitals will have the same symmetry as the HOMO of the product (a hexadiene). The only way to accomplish this is through a conrotatory ring-opening which results in opposite signs for the terminal lobes.
When performing an electrocyclic reaction, it is often desirable to predict the cis/trans geometry of the reaction's product. The first step in this process is to determine whether a reaction proceeds through conrotation or disrotation. The table below shows the selectivity rules for thermal and photochemical electrocyclic reactions.
For the example given below, the thermal reaction of (trans,cis,trans)-octa-2,4,6-triene will happen through a disrotatory mechanism. After determining the type of rotation, whether the product will be cis or trans can be determined by examining the starting molecule. In the example below, the disrotation causes both methyls to point upwards, causing the product to be cis-dimethylcyclohexadiene.
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To develop basic understanding of the reactivity of aromatic and heteroaromatic compounds. To develop a knowledge of a class of pericyclic reactions. To apply them in the context of the synthesis.
A sigmatropic reaction in organic chemistry is a pericyclic reaction wherein the net result is one σ-bond is changed to another σ-bond in an uncatalyzed intramolecular reaction. The name sigmatropic is the result of a compounding of the long-established sigma designation from single carbon–carbon bonds and the Greek word tropos, meaning turn. In this type of rearrangement reaction, a substituent moves from one part of a π-bonded system to another part in an intramolecular reaction with simultaneous rearrangement of the π system.
Vitamin D is a group of fat-soluble secosteroids responsible for increasing intestinal absorption of calcium, magnesium, and phosphate, and many other biological effects. In humans, the most important compounds in this group are vitamin D3 (cholecalciferol) and vitamin D2 (ergocalciferol). The major natural source of the vitamin is synthesis of cholecalciferol in the lower layers of epidermis of the skin, through a photo-chemical reaction of UVB light, from the sun exposure (specifically UVB radiation) or UVB lamps.
Explores light-induced electron transfer dynamics, semiconductors' electrochemical potential, band edge potentials, and pericyclic reactions.
Explores pericyclic reactions, focusing on mechanisms, controls, correlation diagrams, and tools to determine reaction mechanisms.
Explores bond dissociation energies as a measure of radical stability and the impact of substituents on BDE values.
Recent experiments have confirmed the importance of nuclear quantum effects even in large biomolecules at physiological temperature. Here we describe how the path integral formalism can be used to describe rigorously the nuclear quantum effects on equilibr ...
Springer Verlag2010
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Selective cleavages of carbon-carbon bonds catalyzed by transition-metal complexes have been shown to be increasingly versatile tools for organic synthesis allowing for complementary synthetic strategies. Numerous examples of transition-metal catalyzed C-C ...
The path integral methodology for computation of the equilibrium isotope effect is described and applied to three [1,5] sigmatropic hydrogen shift reactions. An efficient estimator for the derivative of the free energy is used, which shortens the computati ...