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Sigmatropic Rearrangement

Delve into the complexities of organic chemistry with this comprehensive article on Sigmatropic Rearrangement. You'll gain a solid understanding of this intriguing subject, from its fundamental definition and characteristics, to its practical applications in different scenarios. Unearth the underlying mechanism, decipher the unique nomenclature, and interpret the step-by-step procedures of Sigmatropic Rearrangement. Providing a holistic insight into an essential aspect of chemistry, this article serves as an indispensable resource for both students and professionals interested in the field of organic chemistry.

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Sigmatropic Rearrangement

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Delve into the complexities of organic chemistry with this comprehensive article on Sigmatropic Rearrangement. You'll gain a solid understanding of this intriguing subject, from its fundamental definition and characteristics, to its practical applications in different scenarios. Unearth the underlying mechanism, decipher the unique nomenclature, and interpret the step-by-step procedures of Sigmatropic Rearrangement. Providing a holistic insight into an essential aspect of chemistry, this article serves as an indispensable resource for both students and professionals interested in the field of organic chemistry.

Understanding Sigmatropic Rearrangement: An Introduction

Sigmatropic rearrangement is a fascinating transformation in organic chemistry, commonly involving the relocation of sigma bonds as well as associated atoms or groups. The impact of this rearrangement on the structure and properties of a molecule can be momentous.

Sigmatropic rearrangement represents a class of pericyclic reaction, unique for the type of migration it involves - the shifting of a sigma bond (σ bond), which occurs between atoms within the same molecule.

Sigmatropic Rearrangement in Organic Chemistry

The concept of sigmatropic rearrangement in organic chemistry is far-reaching. It's a pivotal mechanistic pathway for many reactions, producing an array of organic compounds. It's used to construct and modify molecular architectures in a single step. Let's dive into the formula representing a sigmatropic rearrangement. We can denote it as [i, j] -sigmatropic rearrangement, with 'i' and 'j' being the positions on a chain. This is written mathematically as: \[ \text{[i, j] sigmatropic rearrangement} \] A common example of a sigmatropic rearrangement is the Cope Rearrangement, a [3,3]-sigmatropic reaction involving a 1,5-diene.

In the Cope rearrangement, the following chain shift takes place:

1,5-diene -->
intervening atoms

This reaction occurs via a six-membered transition state, thus allowing for concerted bond breaking and forming. It flits back and forth between two isomeric forms.

Features of Sigmatropic Rearrangement Processes

Sigmatropic rearrangements are noted for several features that shed light on their characteristic behaviours and the range of reactions they enable.
  • They are typically concerted, meaning all the bond-breaking and bond-forming events happen at the same time.
  • They operate under orbital symmetry control, following the Woodward-Hoffmann rules.
  • Temperature effects are prominent in these rearrangements; heating often yields a different product compared to room temperature.
  • They exhibit a unique kinetic isotope effect.
  • Product distribution can be predicted using the Hammond postulate or the Curtin-Hammett principle.
Feature Description
Concerted reaction All bonds break and form simultaneously
Woodward-Hoffmann rules Predicts the stereochemistry of the product
Temperature effects Affects product distribution
Kinetic isotope effect Involves isotopic substituents
Hammond postulate/Curtin-Hammett principle Guides the prediction of product distribution

The Hammond postulate or the Curtin-Hammett principle discusses that the major product of a reaction is not necessarily the most stable one, but the one with the transition state most energetically accessible from the starting material.

Defining Sigmatropic Rearrangement

Sigmatropic rearrangement occurs when a sigma bond in a molecule moves from one position to another, along with the atoms or groups connected to it. This intriguing process allows for the formation of new molecular structures while maintaining the existing bonds' intactness.

The Sigmatropic Rearrangement Definition

In the simplest terms, sigmatropic rearrangement is a pericyclic reaction process where a sigma bond moves within a molecule, causing molecular rearrangement. This σ-bond migration occurs alongside associated atoms or groups. Consequently, the migration results in the formation of new bonds and sigma bonds in previously unconnected parts of the molecule. For a clearer picture, let's denote the process mathematically as: \[ \text{[i, j] sigmatropic rearrangement} \] Here 'i' and 'j' represent the positions of the atoms on a chain involved in the bond shift. The method of representing the rearrangement this way is termed as the Woodward-Hoffmann notation, after the chemists who developed the concept. While discussing sigmatropic rearrangements, it's also essential to consider suprafacial and antarafacial shifts, representing whether a bond's relocation happens on the same face or across different faces of a molecule. Suprafacial Shift: A suprafacial shift implies that the sigma bond migration happens over the same face of the molecule. It's characterised by a bond-breaking and bond-forming process, which occurs without the intermediate changing its overall geometry. Antarafacial Shift: Antarafacial shifts occur when the bond migration occurs on different faces. It's a more complex process, where the intermediate undergoes a significant change before the bond formation takes place.

Fundamental Concepts in Sigmatropic Rearrangement

There are several key concepts that underpin sigmatropic rearrangement and help predict the resultant transformation in the molecular structure. Firstly, the Woodward-Hoffmann rules guide our understanding of sigmatropic rearrangements. These symmetry-based rules act as a compass to navigate the stereochemical outcomes, indicating which products will form under thermal or photochemical conditions. The Woodward-Hoffmann rules are based on certain parameters:
  • The total number of (4n + 2) electrons participating in the reaction.
  • The procedure under which the transformation occurs - thermal or photochemical.
Another critical tenet is the concept of "allowed" and "forbidden" sigmatropic rearrangements. Under thermal conditions:
  • Reactions involving (4n + 2) σ electrons are "allowed".
  • Reactions involving (4n) σ electrons are "forbidden".
However, this does not mean "forbidden" transformations can't occur. They simply have a higher energy barrier and lower rate than "allowed" reactions. We also need to acknowledge the role of the Hammond postulate and the Curtin-Hammett principle in understanding sigmatropic rearrangements. They offer valuable insights into the reaction kinetics and provide a link between the energy of the transition state and the structure of the reaction intermediates. In essence, the depth and breadth of the concepts underpinning sigmatropic rearrangements are as complex as the reactions they explain, offering a profound understanding of what governs the phenomenon of bond migration within molecules.

The Mechanism of Sigmatropic Rearrangement

To understand the true complexity of a sigmatropic rearrangement, it is crucial to delve deeper into the details of its mechanism. This mechanism is the framework that illustrates the path this reaction navigates, demonstrating how such migrations occur in the molecular landscape.

Insight into Sigmatropic Rearrangement Mechanism

Sigmatropic rearrangements have a concerted mechanism, which means they involve simultaneous breaking and forming of bonds. The atoms participating in the reaction stay in a specific geometric arrangement through a cyclic transition state. This transition state, combined with the high degree of symmetry, results in a very particular pattern of connectivity. Take for instance the [3,3]-sigmatropic rearrangement, famously known as the Cope rearrangement. It involves a total of six electrons participating in the concerted mechanism. Before delving into the steps of the mechanism, it's useful to place emphasis on some key features:
  • A six-membered ring transition state is formed.
  • The electrons rotate within the molecule.
  • The rotation is suprafacial, which means that the reacting ends of the sigma bonds stay on the same face of the molecule during the reaction.
  • The Cope rearrangement is a thermally allowed process and is completely reversible.

Interpreting the Steps of Sigmatropic Rearrangement Mechanism

To understand the sigmatropic rearrangement mechanism, let's follow the journey of a molecule undergoing the Cope rearrangement. The mechanism goes as below:
  1. The reaction initiates with the six electrons in the 1,5-diene rotating suprafacially, which means the rotation happens on the same side of the double bonds.
  2. The concerted rotation forms the six-membered transition state. In this stereochemical configuration of the transition state, all six carbon atoms lie in a plane with the hydrogen atoms located alternately above and below the plane.
  3. The reaction progresses through the transition state, with breaking of the initial bond and formation of the new bond.
  4. Finally, the reaction ends up forming isomeric alkene products.
Another example that provides an excellent insight into the sigmatropic rearrangement mechanism is the Claisen rearrangement, a famous [3,3]-sigmatropic rearrangement involving an allyl vinyl ether. In this rearrangement, heating the allyl vinyl ether leads to concerted bond migration, forming a gamma,delta-unsaturated carbonyl compound. The mechanism of the Claisen rearrangement, which also passes through a six-membered transition state, looks something like: \[ \text{Vinyl Ether} \rightarrow \text{Six-membered transition state} \rightarrow \text{Carbonyl Compound} \] The reason these reactions use a six-membered transition state is because such a state allows for the required cyclic delocalisation. It also minimizes the steric interactions involved, rendering the reaction more efficient. Conclusively, the mechanism of the sigmatropic rearrangement underscores the orchestrated dance of bonds and atoms within the molecular sphere, providing us a glimpse of the dynamic nature of the chemical world.

Exploring the Nomenclature of Sigmatropic Rearrangement

The nomenclature of sigmatropic rearrangement is an essential tool for navigating the complex web of reactions and their outcomes. In the realm of organic chemistry, effective communication is key to understanding and articulating concepts accurately. In this regard, the nomenclature of sigmatropic rearrangement plays an integral role.

Deciphering Sigmatropic Rearrangement Nomenclature

As you dive into the world of chemistry, the nomenclature takes on the role of a translator, allowing you to accurately perceive and interpret complex reactions. Sigmatropic rearrangements are no exception. They occur under the umbrella of pericyclic reactions and are denoted by a set of numbers contained within square brackets, such as [i,j]. This is known as the Woodward-Hoffmann notation, named after the brilliant minds who initially developed this system of naming. So, what do these numbers actually mean? Well, here's the secret. The first number 'i' refers to the number of atoms in the moving group of the molecule, while 'j' indicates the atoms on the chain where the group ultimately migrates to. To make this even more clear, let's use this notation to denote [3,3]-sigmatropic rearrangement, commonly known as the Cope rearrangement. Here, a ‘1,5-hexadiene’ structure shifts, resulting in the spatial rearrangement of its atoms, while retaining the original sigma bonds. Understanding this nomenclature is crucial as it helps us to communicate effectively the details of the rearrangement, especially when dealing with complex reactions.

Understanding the Language of Sigmatropic Rearrangement

Just like any language, the nomenclature of sigmatropic rearrangement has its unique syntax and semantics. The Woodward-Hoffmann notational system is inclusive of the suprafacial and antarafacial shift distinction. These shifts infer whether a sigma bond's migration occurs within the same face (suprafacial) or on different faces (antarafacial) in a molecule. The suprafacial and antarafacial terms are denoted by small 's' and 'a' respectively. For example, a [3,3]-suprafacial rearrangement would be denoted as [3s,3s]. Here, both the sigma bond and the migrating group stay on the same face of the molecule throughout the reaction. In contrast, a [3,3]-antarafacial rearrangement would be denoted as [3a,3a]. Here, the sigma bond switch and the migrating group occur on opposite faces of the molecule. This distinction is especially prevalent in the realm of electrocyclic reactions, where the sigma bond migration results in a ring closure—the result of an electrocyclic reaction's concerted, thermal, or photochemical transformation. Particularly in electrocyclic reactions, the Woodward-Hoffmann rules apply:
  • Thermal (4n + 2) - Suprafacial
  • Thermal (4n) - Antarafacial
  • Photochemical (4n + 2) - Antarafacial
  • Photochemical (4n) – Suprafacial
These rules elucidate whether a reaction under thermal or photochemical conditions will occur suprafacially or antarafacially. Comprehending the nomenclature of sigmatropic rearrangement and its supporting terminology provide a streamlined approach to efficient, articulate, and accurate communication of organic reactions. They form a vital part of your chemistry toolbox, empowering you to understand and explore the boundless possibilities of molecular rearrangement.

Practical Examples of Sigmatropic Rearrangement

To genuinely appreciate the magnitude of the science of sigmatropic rearrangement, you'll find it beneficial to examine some practical examples where this chemical process is employed. These instances not only highlight the fundamental importance of sigmatropic reactions but also render them more tangible.

Demonstrating Sigmatropic Rearrangement Examples

Sigmatropic rearrangements play a pivotal role in a wide array of biochemical processes and synthetic pathways. They are routinely employed in the synthesis of complex organic molecules, often facilitating the creation of structures that would be otherwise challenging to obtain. One classic example of the sigmatropic rearrangement is the Claisen Rearrangement. Rolf Claisen, a German chemist, first identified this process in 1912. The beauty of the Claisen rearrangement lies in its transformation of allyl phenyl ether into o-allylphenol via a [3,3]-sigmatropic rearrangement. The reaction is as follows: \[ \text{Allyl phenyl ether}\rightarrow\text{o-Allylphenol} \] Another interesting example of the sigmatropic rearrangement is the Cope Rearrangement. This organic reaction is a prime representation of a [3,3]-sigmatropic rearrangement, named after Arthur C. Cope, who identified it. The Cope rearrangement allows for the interconversion of cis- and trans- isomers. The reaction can be generally represented: \[ \text{cis-Isomer}\rightarrow\text{trans-Isomer} \]

Both reactions above follow a similar transition state. They proceed through a transition state showing a chair conformation. This minimises the steric hindrance in the transition state and helps in smooth facilitation of the reaction.

The Johnson–Claisen rearrangement is another variant of the Claisen rearrangement which consists of an ester linked to an alcohol and a base. In this rearrangement, the alcohol in the ester–alcohol complex migrates to the carbonyl carbon of the ester, thus forming a γ,δ-unsaturated ester. \[ \text{Alcohol-Ester Complex}\rightarrow\text{γ,δ-Unsaturated Ester} \]

Applying Sigmatropic Rearrangement Techniques in Various Scenarios

Sigmatropic rearrangement reactions provide chemists with a repertoire of versatile techniques for complex molecule synthesis. These rearrangements, which can be performed under both mild and harsh conditions, have been employed in the laboratory synthesis of numerous pharmaceuticals and natural products. Sigmatropic rearrangements are also frequently used in the industrial synthesis of polymers, as they allow for the controlled rearrangement of polymer chains. Furthermore, several naturally occurring biochemical processes involve sigmatropic rearrangements. For example, the transformation of squalene to lanosterol, a critical step in the biosynthesis of steroids, involves a series of [1,2]-sigmatropic shifts.

Squalene's transformation into lanosterol is a beautiful dance of atoms that elegantly demonstrates the power of sigmatropic rearrangements in nature. This process forms the backbone of many important biochemical pathways, and understanding its kinetics is vital for understanding the biosynthesis of steroids.

As you can see, the practical applications for sigmatropic rearrangements are vast and varied. Their applicability, combined with their adaptability, makes them an invaluable tool in the toolkit of a chemist, whether it be for creating complex organic molecules, designing new pharmaceuticals, or decoding the chemical magic underpinning nature's own processes.

Sigmatropic Rearrangement - Key takeaways

  • Sigmatropic rearrangement is a pericyclic reaction process where a sigma bond moves within a molecule, resulting in molecular rearrangement and formation of new bonds.
  • Sigmatropic rearrangements follow the Woodward-Hoffmann rules for orbital symmetry control, exhibit a unique kinetic isotope effect, and are typically concerted reactions.
  • Suprafacial and antarafacial shifts are key concepts in Sigmatropic rearrangements, indicating whether a bond's relocation happens on the same face or across different faces of a molecule.
  • The Woodward-Hoffmann notation illustrates the sigmatropic rearrangement, where 'i' and 'j' represent the positions of the atoms on a chain involved in the bond shift.
  • Examples of sigmatropic rearrangement include the Claisen Rearrangement and Cope Rearrangement, where allyl phenyl ether is transformed into o-allylphenol and cis- and trans- isomers are interconverted respectively.

Frequently Asked Questions about Sigmatropic Rearrangement

Sigmatropic rearrangement is a type of organic chemistry reaction in which a sigma bond shifts its location within a molecule. An example is the Cope rearrangement, where the sigma bond in a cyclohexadiene molecule rearranges to form an isomer under increased heat.

Sigmatropic rearrangement involves the shift of a σ-bond (s-bond) across an array of π-bonds (pi-bonds), resulting in a new connectivity of atoms. On the other hand, an electrocyclic reaction involves the formation or breaking of ring systems by the cyclic shift of π-electrons, which doesn't change atom connectivity.

A 3,3 Sigmatropic Rearrangement in chemistry refers to a class of pericyclic reactions where simultaneous bond breakage and formation result in a migration of σ-bonds (sigma bonds). The '3,3' indicates that three pairs of electrons are involved in the bond breaking and forming process.

Sigmatropic rearrangement is a type of molecular rearrangement in chemistry where a sigma bond moves across a pi system. The process usually occurs in a concerted manner, often leading to a change in the connectivity of atoms within a compound.

Sigmatropic rearrangements are named by indicating the number of atoms in the transition state forming the new σ–bond. The notation '[i, j]' is used, where 'i' refers to atoms in the moving group and 'j' indicates atoms in the rest of the molecule.

Test your knowledge with multiple choice flashcards

What is Sigmatropic rearrangement in organic chemistry?

What's the descriptor formula of a sigmatropic rearrangement and an example of such reaction?

What are some key features of the sigmatropic rearrangement processes?

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What is Sigmatropic rearrangement in organic chemistry?

Sigmatropic rearrangement is a class of pericyclic reaction that involves the shifting of a sigma bond within the same molecule. This considerably impacts the molecule's structure and properties.

What's the descriptor formula of a sigmatropic rearrangement and an example of such reaction?

The formula of a sigmatropic rearrangement is denoted as [i, j], where 'i' and 'j' describe the positions on a chain. A common example is the Cope Rearrangement, a [3,3]-sigmatropic reaction involving a 1,5-diene.

What are some key features of the sigmatropic rearrangement processes?

Sigmatropic rearrangements are typically concerted, follow the Woodward-Hoffmann rules, display pronounced temperature effects, showcase a unique kinetic isotope effect and the product distribution can be predicted using the Hammond postulate or the Curtin-Hammett principle.

What is sigmatropic rearrangement in a molecule?

Sigmatropic rearrangement is a pericyclic reaction process where a sigma bond moves within a molecule along with associated atoms or groups, causing molecular rearrangement. This results in the formation of new bonds and sigma bonds in previously unconnected parts of the molecule.

What do 'suprafacial' and 'antarafacial' shifts represent in sigmatropic rearrangements?

'Suprafacial' and 'antarafacial' shifts represent whether a bond's relocation happens on the same face or across different faces of a molecule. A suprafacial shift happens over the same face without changing the overall geometry, while an antarafacial shift occurs on different faces and the intermediate undergoes a significant change.

What are Woodward-Hoffmann rules in the context of sigmatropic rearrangements?

Woodward-Hoffmann rules are symmetry-based guidelines used to predict the products of sigmatropic rearrangements under thermal or photochemical conditions. They consider the total number of (4n + 2) electrons participating and the procedure under which the transformation occurs.

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