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5)
Polyenes contain more than one double bond and are very common in natural
products (ex: carotene). Diene chemistry applies to trienes, tetraenes, etc.
The chemistry of polyenes depends on the relative positions of the C=C bonds:
2) Resonance stabilization:
Electron delocalization contributes to stability of the conjugated diene:
Pi bonding electrons in a conjugated arrangement may resonate between
carbons so the single bonds have some double-bond character:
.. + + ..
H2C CH = CH CH2 H2C = CH HC = CH2 H2C HC = CH CH2
H2C C C CH2
equals resonance hybrid H H
Nomenclature of polyenes (review):
1. Chains and rings are numbered and named in the usual way, starting the numbering at the
end closest to a C = C bond, with an ending of diene or triene, etc.
2. Substituents are numbered accordingly.
CH 3
H
Cl
A side issue: naming compounds with other functional groups in addition to C=C
Such compounds are named as members of the functional group class having priority. Naming
and numbering follows this priority order:
The suffix of the name is the ending for the highest priority group. The position number is
inserted between the root and the suffix. Alkene bonds must also be indicated as part of the
parent chain (or ring) name, with their position number preceding the parent name.
The compound is named as an alcohol, but the presence of the C = C bond must be indicated
by using en in the parent name. Below, the compound is named as an alkene
Example: Cl 2-chloro-5-hexyn-1-ene
Reactions of Dienes: Two Key Types of Reaction
Two situations are possible when more than one C=C is present in a molecule:
A) If they are far apart, both groups may react independently of each other
B) If they are conjugated, the reactivity of one will affect the other
If enough electrophile is present it will react with all the C=C, but when electrophile
is present in short supply, it will add preferentially to the more reactive bond (the
one leading to the more stable carbocation, or surrounded by more R groups)
CH
that the pi-bonding electrons rearrange themselves into new bonds, joining the
diene and the dienophile together in a pericyclic, concerted reaction!
Certain groups of atoms can pull electron density toward themselves through bonds by
the inductive effect. Those groups having a C or N with multiple bonds to an electronegative
atom withdraw e- from dienes through resonance:
O O O O
C C C R C N N
R H R OH R R O
aldehyde acid ketone nitrile nitro
This makes the reaction even more favorable than with unsubstituted dienophile!
If the diene and dienophile are asymmetrical, two structural isomers form.
The Diels-Alder reaction is also stereospecific: that means that any geometric
isomers (for example, cis or trans-alkenes) maintain their configuration: