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Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.

Figure1

The feasibility of cycloaddition reactions under thermal and photochemical conditions can be predicted using a set of selection rules. If the total number of π electrons involved in the rearrangement is a multiple of 4n, the reaction is photochemically allowed. The reaction is thermally allowed if the total number of π electrons involved is 4n + 2.

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CycloadditionPericyclic ReactionDiels Alder Reaction4 2 Cycloaddition2 2 CycloadditionThermal ConditionsPhotochemical ConditionsSelection RulesElectrons

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16.15 : Cycloaddition Reactions: Overview

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16.1 : Structure des diènes conjugués

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16.2 : Stabilité des diènes conjugués

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16.3 : π orbitales moléculaires du 1,3-butadiène

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16.4 : π orbitales moléculaires du cation allyle et de l’anion

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16.5 : π orbitales moléculaires du radical allyle

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16.6 : Addition électrophile de 1,2- et 1,4-HX au 1,3-butadiène

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16.7 : Addition électrophile de 1,2- et 1,4 de x2 à 1,3-butadiène

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16.8 : Ajout électrophile de HX au 1,3-butadiène : contrôle thermodynamique et contrôle cinétique

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16.9 : Spectroscopie UV-Vis des systèmes conjugués

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16.10 : Spectroscopie UV-Vis : règles de Woodward-Fieser

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16.11 : Réactions péricycliques : Introduction

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16.12 : Réactions électrocycliques thermiques et photochimiques : aperçu

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16.13 : Réactions électrocycliques thermiques : stéréochimie

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16.14 : Réactions électrocycliques photochimiques : stéréochimie

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