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Chapter 16: Dienes, Conjugated Pi Systems, and Pericyclic Reactions Back To Chapter

16.13: Thermal Electrocyclic Reactions: Stereochemistry

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Thermal Electrocyclic Reactions: Stereochemistry

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16.12: Thermal and Photochemical Electrocyclic Reactions: Overview

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16.14: Photochemical Electrocyclic Reactions: Stereochemistry

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Thermal electrocyclic reactions proceed via the ground state HOMO of the conjugated system. The stereochemical outcome depends on the mode of ring closure and the number of π electrons.

For example, consider the electrocyclization of a triene containing six π electrons and a diene with four π electrons.

Let's examine the mode of ring closure in both systems under thermal conditions.

The ground state HOMO of the triene has two nodes and symmetric terminal lobes. For the bond to form, the terminal lobes must overlap constructively. This can only happen if both lobes rotate in opposite directions, favoring a disrotatory ring closure and a cis product.

In comparison, the ground state of the diene has one node and antisymmetric terminal lobes. Here, the lobes must rotate in the same direction to form the new σ bond, resulting in a conrotatory ring closure and a trans product.

In summary, thermally allowed electrocyclic reactions are disrotatory if the number of π electron pairs is odd and conrotatory if it is even.

16.13: Thermal Electrocyclic Reactions: Stereochemistry

The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.

Selection Rules: Thermal Activation

Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.

Conjugated systems with an odd number of π-electron pairs undergo a disrotatory ring closure. For example, (2E,4Z,6E)-2,4,6-octatriene, a conjugated diene containing three π-electron pairs, yields cis-5,6-dimethyl-1,3-cyclohexadiene.

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Thermal Electrocyclic Reactions Stereochemistry Orbital Symmetry Polyene HOMO Thermal Conditions Ground-state HOMO Selection Rules Thermal Activation Conrotatory Ring Closure Disrotatory Ring Closure Conjugated Systems Even Number Of &960;-electron Pairs Odd Number Of &960;-electron Pairs

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