synthesis of heterocyclic rings 7 (cycloaddition reactions)
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Synthesis of Heterocyclic Rings 7 (Cycloaddition Reactions)
A cycloaddition is a pericyclic 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."[1]
a pericyclic reaction is a type of organic reaction wherein the transition state of the molecule has a cyclic geometry,
µ-electrons Reaction(Geometry)
Cycloaddition
2+2 Chelotropic1 + 2 = 3
2+2 2+22+ 2 = 4
2+4 Chelotropic2 + 4 = 5
2+4 1,3-dipolar cycloaddition2+ 3 = 5
2+4 Diels-Alder2+4 = 6
1,3-Dipolar Cycloaddition Reactions
Resonance Structures of 1,3-DipolesEach molecule has at least one resonance structure which indicates
separation of opposite charges in 1,3-relationship.
Mechanism of Cycloaddition:1,3-Dipolar cycloaddition reactions were found to be stereoselective.
Most of them are regioselective.
Orbital picture of 1,3-dipoles and dipolarophiles
Concerted mechanism: one step mechanism in which two bonds are formed at the same time (Huisgen)
Biradical mechanism (Stepwise mechanism) (Firestone)
XY
z
R
H H
R
Y
RR
zX
YX
RR
zY
X
RR
z
Y
RR
zX
+
-+
.
..
.
+
+
Regiochemistry: orbitals of the same size interact
Generation of 1,3-DipolesNitrile oxides
Nitrile Sulfides
Nitrile Imides (Nitrilimines)