Cycloaddition: Difference between revisions

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A '''cycloaddition''' is a [[chemical reaction]], in which "two or more unsaturated molecules (or parts of the same molecule) combine with the formation of a cyclic adduct in which there is a net reduction of the bond multiplicity." The resulting reaction is a [[cyclization]] reaction. Many but not all cycloadditions are [[Concerted reaction|concerted]] and thus [[pericyclic]].<ref name="goldbook">{{Citation|title=cycloaddition|url=https://goldbook.iupac.org/html/C/C01496.html|work=IUPAC Compendium of Chemical Terminology|publisher=IUPAC|doi=10.1351/goldbook.C01496|access-date=2018-10-13}}</ref> Nonconcerted cycloadditions are not pericyclic.<ref>{{Citation|title=pericyclic reaction|url=https://goldbook.iupac.org/html/P/P04491.html|work=IUPAC Compendium of Chemical Terminology|publisher=IUPAC|doi=10.1351/goldbook.P04491|access-date=2018-10-13}}</ref> As a class of [[addition reaction]], cycloadditions permit carbon–carbon bond formation without the use of a [[nucleophile]] or [[electrophile]].

Cycloadditions can be described using two systems of notation. An older but still common notation is based on the size of linear arrangements of atoms in the reactants. It uses [[parentheses]]: (''i'' + ''j'' + …...) where the variables are the numbers of linear atoms in each reactant. The product is a cycle of size (''i'' + ''j'' + …...). In this system, the standard [[Diels-Alder reaction]] is a (4 + 2)-cycloaddition, the [[1,3-dipolar cycloaddition]] is a (3 + 2)-cycloaddition and [[cyclopropanation]] of a carbene with an alkene a (2 + 1)-cycloaddition.<ref name=goldbook />

A more recent, IUPAC-preferred notation, first introduced by [[Robert Burns Woodward|Woodward]] and [[Roald Hoffmann|Hoffmann]], uses [[square brackets]] to indicate the number of ''electrons'', rather than carbon atoms, involved in the formation of the product. In the [''i'' + ''j'' + …...] notation, the standard Diels-Alder reaction is a [4 + 2]-cycloaddition, while the 1,3-dipolar cycloaddition is also a [4 + 2]-cycloaddition.<ref name=goldbook />

==Thermal cycloadditions and their stereochemistry==