16.11
Reacciones pericíclicas: introducción
Las reacciones pericíclicas son reacciones orgánicas que ocurren mediante un mecanismo concertado sin generar intermediarios. Las reacciones proceden…
Según el mecanismo, las reacciones orgánicas se pueden clasificar en términos generales como iónicas, radicales y pericíclicas. Mientras que las reacciones iónicas y radicales tienen intermedios bien definidos, las reacciones pericíclicas proceden sin ningún intermediario.
Hay tres clases de reacciones pericíclicas: reacciones electrocíclicas, reacciones de cicloadición y reordenamientos sigmatrópicos.
En una reacción electrocíclica, los extremos de un sistema de π conjugados se unen para formar un nuevo enlace σ, lo que da como resultado un producto cíclico con un enlace π menor que el reactivo.
En las reacciones de cicloadición, dos sistemas π diferentes interactúan para formar un anillo, con dos enlaces π de los reactivos, transformándose en dos nuevos enlaces σ.
Un reordenamiento sigmatrópico implica el movimiento neto de un enlace σ de una posición a otra.
A diferencia de las reacciones iónicas o radicales, las reacciones pericíclicas son concertadas, involucrando un flujo de electrones en una trayectoria circular que conduce a un estado de transición cíclico.
Por último, se activan térmica o fotoquímicamente y muestran una alta estereoespecificidad.
View the full transcript and gain access to JoVE Core videos
Q1: What are the three main classes of pericyclic reactions?
Pericyclic reactions are classified into three categories: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. Electrocyclic reactions involve the ends of a conjugated π system joining to form a new σ bond, resulting in a cyclic product. Cycloaddition reactions occur when two different π systems interact to form a ring. Sigmatropic rearrangements involve the net movement of a σ bond from one position to another.
Q2: How do pericyclic reactions differ from ionic and radical reactions?
Unlike ionic and radical reactions, which have well-defined intermediates, pericyclic reactions proceed without any intermediates. Pericyclic reactions are concerted, involving a flow of electrons in a circular path leading to a cyclic transition state. This concerted mechanism and absence of intermediates fundamentally distinguish pericyclic reactions from other organic reaction types.
Q3: What is the role of electron flow in pericyclic reaction mechanisms?
In pericyclic reactions, electrons flow in a closed loop to form a cyclic transition state, where rearrangement of σ and π bonds yields specific products. This circular electron movement is the defining feature of the concerted mechanism. The pathway of electron flow determines the stereochemistry and regiochemistry of the products formed.
Q4: Why are pericyclic reactions stereospecific?
Pericyclic reactions are stereospecific because the product configuration depends on the number of electrons participating in the reaction and the π molecular orbital symmetries of the reactants and products. The concerted mechanism and cyclic transition state ensure that only one stereoisomer is formed. This predictable stereochemistry makes pericyclic reactions valuable in organic synthesis.
Q5: What activation methods are used for pericyclic reactions?
Pericyclic reactions are thermally or photochemically activated, meaning they can be driven by heat or light energy. Unlike ionic or radical reactions, they do not require catalysts and are not influenced by solvent polarity. The choice between thermal and photochemical activation depends on the specific reaction and desired product selectivity.
Q6: What is the difference between intramolecular and intermolecular pericyclic reactions?
Electrocyclic reactions and sigmatropic rearrangements are intramolecular pericyclic reactions, occurring within a single molecule. Cycloaddition reactions are intermolecular processes, involving two separate reactant molecules. The classification depends on whether the reaction involves one molecule rearranging or two molecules combining to form a ring.
Q7: How do bond changes distinguish the three pericyclic reaction classes?
The three pericyclic reaction classes differ in the number and type of bonds broken and formed. In electrocyclic reactions, one π bond breaks to form one σ bond. In cycloaddition reactions, two π bonds break to form two σ bonds. In sigmatropic rearrangements, no π bonds break; instead, a σ bond migrates with simultaneous rearrangement of adjacent π bonds.