Pericyclic reaction

In organic chemistry, a pericyclic reaction is a type of organic reaction wherein the transition state of the molecule has a cyclic geometry, and the r reaction progresses in a concerted fashion. Pericyclic reactions are usually rearrangement reactions. . The major classes of pericyclic reactions are:

Electrocyclic reactions Cycloadditions Sigmatropic reactions Group transfer reactions Cheletropic reactions Dyotropic reactions

In general, these are considered to be equilibrium processes processes, , although it is possible to push the reaction in one direction by designing a reaction by which the product is at a significantly lower energ energy level; this is due to a unimolecular interpretation of Le Chatelier's principle principle. Pericyclic reactions often have related stepwise radical processes associated with them. Some pericyclic reactions, such as the [2+2] cycloaddition, are 'controversial' because their mechanism is not definitively known to be concerted (or or may depend on the reactive system.

Pericyclic reactions in biochemistry

Pericyclic reactions also occur in several biological processes.

Claisen rearrangement of chorismate to prephenate in almost all prototrophic organisms. [1,5]-sigmatropic shift in the transformation of precorrin-8x to hydrogenobyrinic acid non-enzymatic, photochemical electrocyclic ring opening and a (1,7) sigmatropic hydride shift in vitamin D synthesis. a conversion of Isochorismate into salicylate and Pyruvate in a catalyzed, true pericyclic reaction.

1. Electrocyclic reaction
pericyclic rearrangement reaction where the net result is one pi bond being converted into one sigma bond or vice-versa. versa. These reactions are usually unnamed, being categorized by the following criteria:

electrocyclic reactions are photoinduced or thermal the number of pi electrons in the species with more pi bonds determines reaction mode electrocyclic reaction can be a ring closure ( ) or a ring opening reaction the stereospecifity is determined by conrotatory or disrotatory mode of transition state formation as predicted by the Woodward-Hoffmann Hoffmann rules rules.

The torquoselectivity in an electrocyclic reaction refers to the direction of rotation. For example, a reaction that is conrotatory can still rotate in two directions, producing enantiomeric products. A reaction that is torquoselective restricts one of these directions of rotation (partially or completely) to produce a product in enantiomeric excess. The Nazarov cyclization reaction is a named electrocyclic reaction converting divinylketones to cyclopentenones. A classic example is the thermal ring-opening ring reaction of 3,4-dimethylcyclobutene. dimethylcyclobutene. The cis isomer exclusively yields cis,trans-2,4-hexadiene hexadiene whereas the trans isomer gives the trans,trans diene: diene

This reaction course can be explained in a simple analysis through the frontier-orbital orbital method 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 butadiene). ). The only way to accomplish this is through a conrotatory ringopening which results in opposite signs for the terminal lobes.

Woodward-Hoffman Rules

Correlation diagrams, which connect the molecular orbitals of the reactant to those of the product having the same symmetry, can then be constructed for the two processes. Frontier molecular orbital Theory According to the Frontier Molecular Orbital Theory, the sigma bond in the ring will open in such a way that the resulting p-orbitals will have the same symmetry as the HOMO of the product.

For the 5,6-dimethylcyclohexa-1,3-diene, only a disrotatory mode would result in p-orbitals having the same symmetry as the HOMO of hexatriene. For the 3,4-dimethylcyclobutene, on the other hand, only a conrotatory mode would result in p-orbitals having the same symmetry as the HOMO of butadiene. Electrocyclic Reactions in Biological Systems Electrocyclic reactions occur frequently in nature.One of the most common such electrocyclizations is the biosynthesis of vitamin D3.

The first step involves a photochemically induced conrotatory ring opening of 7 7-dehydrocholesterol dehydrocholesterol to form pre vitamin D3. A [1,7]-hydride hydride shift then forms vitamin D3.Another example is in the proposed biosynthesis of aranotin, a naturally occurring oxepine, and its related compounds.

2.Cycloaddition
A cycloaddition is a pericyclic chemical reaction reaction, , in which "two or more unsaturated molecules (or parts of the same molecule) ) combine with the formation of a cyclic adduct in which there is a net reduction of the bond multiplicity." The resulting reaction is a cyclization reaction. Cycloadditions are usually y described by the backbone size of the participants. This would make the DielsAlder reaction a [4 + 2]cycloaddition, and the 1,3-dipolar cycloaddition a [3 + 2]cycloaddition. This type of reaction is non-polar addition reaction reaction. Reaction mechanism Thermal cycloadditions usually have (4n + 2) electrons participating in the starting material, for some integer n. These occur, for reasons of orbital symmetry, in a suprafacial-suprafacial suprafacial or antarafacialantarafacial manner (rare). There are a few examples of thermal cycloadditions which have 4n electrons (for example the [2 + 2] cycloaddition); these proceed in a suprafacial suprafacial-antarafacial antarafacial sense, such as the dimerisation of ketene, in which the orthogonal set of p orbitals allows the reaction to proceed via a crossed transition state. Types of cycloaddition
Diels-Alder reactions

The Diels-Alder reaction is a [4+2]cycloaddition reaction.

Huisgen cycloadditions

The Huisgen cycloaddition reaction is a [2+3]cycloaddition.

Nitrone-olefin cycloaddition

The Nitrone-olefin cycloaddition is a [3+2]cycloaddition.

3.Sigmatropic reaction
A sigmatropic reaction in organic chemistry is a pericyclic reaction wherein the net result is one -bond is changed to another -bond in an uncatalyzed intramolecular process. 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 -bonded system to another part in an intramolecular reaction with simultaneous rearrangement of the system. True sigmatropic reactions are usually uncatalyzed, although lewis acid catalysis is possible. Sigmatropic reactions often have transition-metal catalysts that form intermediates in analogous reactions. The most well-known of the sigmatropic rearrangements are the [3,3] Cope rearrangement, Claisen rearrangement, Carroll rearrangement and the Fischer indole synthesis.

4.Group transfer reaction

Group transfer reactions are pericyclic reactions where one pi bond is converted to one sigma bond, at the same time that a sigma bond migrates. The best known group transfer reaction is the ene reaction.

5.Cheletropic reaction
Cheletropic reactions are a type of pericyclic reaction. A pericyclic reaction is one that involves a transition state with a cyclic array of atoms and an associated cyclic array of interacting orbitals. A reorganization of and bonds occurs in this cyclic array. Specifically, cheletropic reactions are a subclass of cycloadditions. The only difference is that on one of the reagents, both new bonds are being made to the same atom.A few examples are shown to the right. In the first case, the single atom is the carbonyl carbon that ends up in carbon monoxide. The end result is making two new bonds to one atom. The first two examples are known as cheletropic extrusions because a small stable molecule is given off in the reaction. The driving force for these reactions is often the entropic benefit of gaseous evolution (e.g. CO or N2).

6.Dyotropic reaction
A dyotropic Reaction (from the Greek dyo, meaning two) in organic chemistry is a type of organic reaction and more specifically a pericyclic valence isomerization in which two sigma bonds simultaneously migrate intramolecularly. The reaction type is of some relevance to organic chemistry because it can explain how certain reactions occur and because it is a synthetic tool in the synthesis of organic molecules for example in total synthesis.