Dienes & Polyenes: An overview and some key reactions (Ch. 14.1-14.

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:

CH3 HC = CH HC = CH CH3 H2C = CH CH2 CH2 HC = CH2

conjugated dienes have specific reactions isolated dienes behave
like regular alkenes
CH3 HC = C = CH CH2 CH3
cumulated dienes are less common

Stability: Based on heats of hydrogenation, the trend in relative stabilities is:

conjugated dienes > isolated dienes > cumulated dienes

Why should the positions of the pi bonds matter?

1) Hybridization and orbital overlap:

-- All C = C double bonds have sp2 sp2 overlap
-- C C single bonds in between puts sp3 hybrids in the overlap
-- The greater the s character in each hybrid, the better the overlap
-- Can also be explained by MOs as shown in fig. 14.2
-- Result is greater stability in the conjugated dienes, less in the isolated.

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

Common names: H2C = C = CH2 allene isoprene

(E/Z) isomerism in dienes:

For any dienes except those with terminal C = C bonds or identical groups
on a single C, there will be E/Z isomerism at both C = C bonds.
The E or Z configuration at each double bond, preceded by its bond position
number, appears at the beginning of the name
CH3
How many H2
configurations H3C C C C C C CH3
are possible for: H H H

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:

C=O > OH > NH2 > C=C > C=C

ketones, aldehydes alcohols amines alkenes
alkynes

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.

Example: CH3CH2-HC = CH-CH2OH 2-penten-1-ol

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

I. Reaction type: Electrophilic addition

Reactivity: Dienes are nucleophilic just like alkenes & alkynes

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

(A) Electrophilic additions to isolated dienes resemble those of regular alkenes.

-- Addition of H X produces alkyl halides with Markovnikov orientation

-- Acid-catalyzed addition of water and oxymercuration produce alcohols with
Markovnikov orientation, alkoxymercuration produces ethers
-- Hydroboration produces alcohols with anti-Markovnikov orientation
-- Hydrogenation produces at least some saturated bonds

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)

(B) Electrophilic additions to conjugated dienes form mixtures of products due to

the resonance of the allylic carbocations

Ex: CH2=CH-CH=CH2 + HBr H2C=CH-CH-CH3 + BrCH2-HC=CH-CH3

Br
1,3-butadiene 1,2 addition 1,4 addition
II. Reaction Type: Cycloaddition (The Diels-Alder Reaction)
Reactivity: Diene acts as donor and acceptor

When a conjugated diene meets a dienophile, the attraction is so strong

CH

that the pi-bonding electrons rearrange themselves into new bonds, joining the
diene and the dienophile together in a pericyclic, concerted reaction!

The Diels-Alder cycloaddition

results in 2 new bonds, with one bond moving to a new position

occurs when a diene meets an alkene or alkyne, particularly one with an

electron-withdrawing group attached to the C = C

results in formation of a new 6-membered ring of C atoms

is actually a 1,4-addition reaction

requires the diene to have both bonds in an s-cis configuration

occurs spontaneously with the right dienophile

Electron withdrawing groups?

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:

Note that in the product, one additional ring is formed.

If you start with a cyclic compound:

cyclic diene + dienophile = bridged bicyclic compound

In some situations, approach of the dienophile may occur in two orientations,

leading to an exo or endo configuration (exo has the substituent pointing toward
the sp3 bridge)
Product formation relies on the correct overlap of orbitals in the diene &
dienophile.
An example is this reaction, which you will perform in the lab.

Proper positioning of pi-bonding orbitals is key! The predominant product is the

endo isomer: cis-norbornene-5,6-endo-dicarboxylic anhydride.