30.3 Stereochemistry of Thermal Electrocyclic Reactions
2 min read•may 7, 2024
Thermal are fascinating transformations in organic chemistry. They involve the opening or closing of rings in conjugated systems, with dictated by orbital symmetry and electron pair count.
Understanding these reactions is crucial for predicting product structures. The provide a framework for determining whether a reaction will proceed through or pathways, based on molecular orbital theory.
Stereochemistry of Thermal Electrocyclic Reactions
Stereochemistry in thermal electrocyclic reactions
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- predicts reactivity and stereochemical outcomes
- Highest Occupied Molecular Orbital () and ###Lowest_unoccupied_molecular_orbital_()_0### are key determinants
- HOMO symmetry dictates disrotatory or conrotatory reaction pathways ( symmetry)
- HOMO symmetry determines stereochemical course
- (s) HOMO leads to disrotatory ring-opening/closure (, )
- (a) HOMO results in conrotatory ring-opening/closure ()
- Assigning HOMO symmetry involves comparing terminal p orbital phases
- Like phases (both shaded or unshaded) indicate symmetric (s) HOMO
- Opposite phases (one shaded, one unshaded) signify antisymmetric (a) HOMO
- Priority assignment to polyene ends (1 and 2) aids in determining symmetry
- Woodward-Hoffmann rules provide a framework for predicting stereochemical outcomes in these reactions
Electron pairs and ring transformations
- Electron pair count in conjugated polyene system dictates ring-opening/closure mode
- Double bonds and lone pairs contribute to the electron pair tally
- Even electron pairs (4n) undergo conrotatory transformations
- Cyclobutene (4 electron pairs) exhibits conrotatory ring-opening to 1,3-butadiene
- Electrocyclization of 1,3-butadiene yields cyclobutene via conrotatory closure
- Odd electron pairs (4n+2) follow disrotatory pathways
- (6 electron pairs) cyclizes disrotatorily to
- Disrotatory ring-opening of 1,3-cyclohexadiene generates 1,3,5-hexatriene
Product prediction for specific reactions
- Conjugated trienes (4n+2) undergo disrotatory ring-closure
- 1,3,5-Hexatriene showcases antisymmetric HOMO
- Disrotatory electrocyclization yields cis-1,3-cyclohexadiene
- Substituent orientation in product depends on specific disrotatory motion
- Cyclobutenes (4n) exhibit conrotatory ring-opening
- possesses symmetric HOMO
- Conrotatory opening generates
- Stereochemistry of substituents in diene product governed by conrotatory rotation
- Stereochemical outcome relies on electron pair count and associated rotational mode
- Disrotatory for 4n+2 systems, conrotatory for 4n systems
- Terminal substituent rotation during ring-opening/closure defines product stereochemistry
Pericyclic Reactions and Mechanisms
- Electrocyclic reactions are a subset of
- These reactions proceed through a
- provides the energy needed for the reaction to occur
- help visualize electronic rearrangements during the reaction
- reactions, such as Diels-Alder reactions, are another important class of pericyclic reactions
Key Terms to Review (27)
1,3-cyclohexadiene: 1,3-cyclohexadiene is a cyclic organic compound consisting of a six-membered carbon ring with two double bonds located at the 1 and 3 positions. It is an important intermediate in many organic reactions, particularly those involving thermal electrocyclic reactions.
1,3,5-hexatriene: 1,3,5-hexatriene is a conjugated polyene with six carbon atoms and three carbon-carbon double bonds arranged in an alternating pattern. It is a key term that is important in understanding the stability of conjugated dienes, the molecular orbitals of conjugated pi systems, the stereochemistry of thermal electrocyclic reactions, and the photochemical electrocyclic reactions.
3,4-dimethylcyclobutene: 3,4-dimethylcyclobutene is a cyclic organic compound with four carbon atoms and two methyl (CH3) substituents attached to the third and fourth carbon positions of the cyclobutene ring. It is a simple cycloalkene that is relevant in the context of understanding the stereochemistry of thermal electrocyclic reactions.
Anti stereochemistry: Anti stereochemistry describes the spatial arrangement in a chemical reaction where two substituents are positioned on opposite sides of a double bond or ring structure after the reaction. It is particularly relevant in the halogenation of alkenes, resulting in products where the added atoms are located across from each other.
Antisymmetric: Antisymmetric is a property of a mathematical function or operator where the function changes sign when the order of its arguments is reversed. This concept is particularly relevant in the context of thermal electrocyclic reactions, where the stereochemistry of the reaction products is influenced by the antisymmetric nature of the molecular orbitals involved.
Butadiene: Butadiene is a simple conjugated diene compound with the chemical formula C₄H₆. It is a colorless, volatile gas that is widely used in the production of synthetic rubber and other polymers. Butadiene is particularly relevant in the context of the stereochemistry of thermal electrocyclic reactions.
Concerted Mechanism: A concerted mechanism refers to a reaction that occurs in a single, continuous step without the formation of any discrete intermediates. In a concerted mechanism, the bonds that are being formed and broken happen simultaneously, leading to the product in a single, coordinated process.
Conrotatory: Conrotatory refers to the stereochemical outcome of a pericyclic reaction, specifically an electrocyclic reaction, where the substituents on the reacting system rotate in the same direction during the cyclization or cycloreversion process.
Cycloaddition: Cycloaddition is a fundamental organic chemistry reaction in which two or more unsaturated molecules, or parts of the same molecule, combine to form a cyclic adduct. This process is a powerful tool for the synthesis of a wide range of carbocyclic and heterocyclic compounds, and it is particularly important in the context of alkene oxidation, carbene addition, the Diels-Alder reaction, and various thermal electrocyclic and cycloaddition reactions.
Cyclobutene: Cyclobutene is a cyclic organic compound with a four-membered ring consisting of three carbon atoms and one double bond. This structural feature makes cyclobutene an important molecule in the context of electrocyclic reactions, which involve the interconversion between cyclic and acyclic (open-chain) compounds.
Diels–Alder cycloaddition reaction: The Diels–Alder cycloaddition reaction is a chemical process in organic chemistry where a conjugated diene reacts with a substituted alkene (dienophile) to form a six-membered ring. This reaction occurs through a single, concerted step without the formation of intermediates.
Disrotatory: Disrotatory refers to the stereochemical outcome of an electrocyclic reaction where the substituents on the reacting system rotate in opposite directions during the cyclic interconversion. This term is particularly relevant in the context of understanding the stereochemistry of thermal and photochemical electrocyclic reactions.
Electrocyclic Reactions: Electrocyclic reactions are a class of pericyclic reactions in organic chemistry that involve the formation or cleavage of a cyclic structure through the concerted movement of $\pi$ electrons. These reactions play a crucial role in the synthesis and interconversion of various organic compounds.
Frontier Orbital Theory: Frontier Orbital Theory is a conceptual framework in organic chemistry that explains the stereochemistry and reactivity of thermal electrocyclic reactions. It focuses on the behavior and interactions of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) during these pericyclic processes.
Hexatriene: Hexatriene is a conjugated hydrocarbon molecule consisting of six carbon atoms and three double bonds. It is a key intermediate in various thermal electrocyclic reactions and plays a crucial role in understanding the stereochemistry of these processes.
HOMO: HOMO, or Highest Occupied Molecular Orbital, is a fundamental concept in molecular orbital theory that describes the highest energy level occupied by electrons in a molecule. This term is crucial in understanding the stability, reactivity, and spectroscopic properties of organic compounds, particularly in the context of conjugated systems, pericyclic reactions, and the chemistry of vision.
Homotopic: In the context of 1H NMR spectroscopy and proton equivalence, homotopic protons are those that can be interchanged by a symmetry operation without changing the molecule's overall spatial arrangement. These protons have identical chemical environments and therefore exhibit identical chemical shifts in NMR spectroscopy.
Lowest unoccupied molecular orbital (LUMO): The LUMO is the lowest energy molecular orbital that does not contain electrons but can accept them during chemical reactions or excitations. It plays a crucial role in determining the reactivity and properties of molecules, especially in conjugated systems analyzed by ultraviolet spectroscopy.
LUMO: LUMO, or Lowest Unoccupied Molecular Orbital, is a fundamental concept in molecular orbital theory that describes the energy level of the highest-energy orbital that is not occupied by electrons in the ground state of a molecule. The LUMO is crucial in understanding the stability and reactivity of conjugated systems, as well as the behavior of molecules in various photochemical and pericyclic reactions.
Orbital Correlation Diagrams: Orbital correlation diagrams are visual representations that illustrate the correlation between the orbital interactions and the stereochemical outcome of thermal electrocyclic reactions. These diagrams provide a clear understanding of how the symmetry and phase relationships of the involved molecular orbitals dictate the stereochemistry of the product formation.
Pericyclic Reactions: Pericyclic reactions are a class of organic reactions that involve the concerted rearrangement of pi-electrons within a cyclic transition state. These reactions are characterized by their unique mechanism, which allows for the formation or cleavage of cyclic structures through the simultaneous breaking and forming of chemical bonds.
Photochemical reactions: Photochemical reactions are chemical reactions initiated by the absorption of light energy, specifically ultraviolet or visible light, leading to the transformation of molecules. These reactions are integral in organic chemistry for creating new molecular structures with desired stereochemistry.
Stereochemistry: Stereochemistry is the study of the three-dimensional arrangement of atoms in molecules and how this arrangement affects the chemical and physical properties of the substance. It examines the spatial orientation of atoms and their relationship to one another, which is crucial in understanding many organic chemistry concepts.
Symmetric: Symmetric refers to a property where an object or structure exhibits a balanced, mirrored arrangement about one or more axes. In the context of organic chemistry, symmetry plays a crucial role in understanding the stereochemistry of thermal electrocyclic reactions.
Thermal Activation: Thermal activation refers to the process by which a chemical reaction is initiated or accelerated by the input of thermal energy, such as heat. This concept is particularly relevant in the context of understanding the stereochemistry of thermal electrocyclic reactions and the mechanisms of sigmatropic rearrangements.
Trans-2,4-hexadiene: trans-2,4-hexadiene is a conjugated diene with a trans configuration between the second and fourth carbon atoms. It is an important compound in the study of stereochemistry of thermal electrocyclic reactions, as its behavior under thermal conditions provides insights into the principles governing the stereochemical outcomes of these reactions.
Woodward-Hoffmann Rules: The Woodward-Hoffmann rules are a set of principles that describe the stereochemical outcomes of pericyclic reactions, such as electrocyclic reactions, cycloadditions, and sigmatropic rearrangements. These rules provide a framework for predicting the feasibility and stereochemistry of these types of organic reactions based on the topology of the molecular orbitals involved.