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Organic Chemistry II TA: Robert Spencer

Ch. 12: Dienes and the Allyl System: 2 p Orbitals in Conjugation

C o nju g at ed Die n es A diene is conjugated when its coplanar double bonds are separated by a single bond. Conjugated dienes are generally stable due to the delocalization of pi electrons along sp 2 hybridized orbitals.

of pi electrons along sp 2 hybridized orbitals. = H C C C H H H

=

H C C C H
H
C
C
C
H

H

H

along sp 2 hybridized orbitals. = H C C C H H H 1,3-Butadiene: Conjugated =

1,3-Butadiene: Conjugated

=

orbitals. = H C C C H H H 1,3-Butadiene: Conjugated = 1,4-Pentadiene: Isolated = Propadiene

1,4-Pentadiene: Isolated

=

H H H 1,3-Butadiene: Conjugated = 1,4-Pentadiene: Isolated = Propadiene (Allene): Cumulated 1 , 3 -Bu

Propadiene (Allene): Cumulated

1 , 3 -Bu t a d ien e R es o n an c e

(Allene): Cumulated 1 , 3 -Bu t a d ien e R es o n an
(Allene): Cumulated 1 , 3 -Bu t a d ien e R es o n an
(Allene): Cumulated 1 , 3 -Bu t a d ien e R es o n an

Lowest

Energy

Highest

Energy

1 , 3 -Bu t a d ien e M o lecu la r O rb it als

Electron delocalization always leads to lower energy and greater stability. Due to an interaction between the pi orbitals of 1,3-butadiene's double bonds, the single bond is stronger and shorter than a typical single bond.

double bonds, the single bond is stronger and shorter than a typical single bond. double-bond character
double bonds, the single bond is stronger and shorter than a typical single bond. double-bond character

double-bond

character

double bonds, the single bond is stronger and shorter than a typical single bond. double-bond character

Alle n es in th e Iso mer iza t io n o f Ac et y len e s

1. NaNH 2 / NH 3 2. H 2 O Mechanism: H 3 C C
1. NaNH 2 / NH 3
2. H 2 O
Mechanism:
H 3 C
C
C
CH
2
H 3 C
H
NH 2
NH 3
H 3 C
C
C
CH 3
C
C
C
H
H
H 3 C
C
C
CH
2
NH 2
C
H 3
pKa = 26
C
C
C
H
NH 2
NH 3
H
H 2
H 2
C C
C
C
C
C
H
C
H 3
C
H 3 C
H 3
NH 2
C
C
C
H
H 2 O
H
H 2
C C
C
H

H 3

C

Ele ct r op h ilic Ad d it io n s to C o nju g at ed D ien es

4 2 1 3
4
2
1
3
H Cl
H
Cl
Cl
Cl

Cl

it io n s to C o nju g at ed D ien es 4 2

1,2-Addition

+

Cl
Cl
1,4-Addition
1,4-Addition

Cl

Reaction Temp: 25 o C

40%

60%

-80 o

C

80%

20%

Kinetic Product

Thermodynamic Product

The 1,4-product is more stable because its double bond is more substituted; however, this product requires crossing a higher energy transition state.

Kinetic control favors the product of 1,2-addition. This might be explained by the location of the chloride ion immediately following protonation.

H

Cl
Cl
of the chloride ion immediately following protonation. H Cl Many other electrophiles can also add to

Many other electrophiles can also add to conjugated dienes:

Br Br
Br
Br
Br
Br

Br

Br
Br
Br Br
Br
Br

Brcan also add to conjugated dienes: Br Br Br Br Br Br Br Br Br Br

can also add to conjugated dienes: Br Br Br Br Br Br Br Br Br Br

Brcan also add to conjugated dienes: Br Br Br Br Br Br Br Br Br Br

also add to conjugated dienes: Br Br Br Br Br Br Br Br Br Br Br

Bralso add to conjugated dienes: Br Br Br Br Br Br Br Br Br Br Low

Br

Low Temp

(Kinetic)

Br Br Br Br Br Br Br Br Br Br Br Low Temp (Kinetic) High Temp

High Temp (Thermodynamic)

Br

Th e Ally l Sy st em

(Kinetic) High Temp (Thermodynamic) Br Th e Ally l Sy st em Ef fects of delocalization:

Ef fects of delocalization:

1. Allylic Halides (S N 1): Resonance stabilization of allyl

cation increases reactivity of allyl halides.

2. Allyl Halides (S N 2): Transition state lies at lower energy,

which leads to an accelerated reaction.

Molecular Orbitals:

which leads to an accelerated reaction. Molecular Orbitals: Antibonding Carbanion LUMO Nonbonding Carbocation LUMO

Antibonding Carbanion LUMO

Nonbonding Carbocation LUMO

Bonding

Energy

3. Allyl Radicals: Resonance favors the formation of an allylic radical (i.e. NBS Mechanism).

Diels -Ald er R eac tio n o f Die n es General Mechanism: Diene
Diels -Ald er R eac tio n o f Die n es
General Mechanism:
Diene
Dienophile

In this exothermic reaction, a conjugated diene reacts with an alkene or alkyne (dienophile) to f orm a six- membered ring.

Diene: Require s-cis conformation

s-trans s-cis
s-trans
s-cis

Unreactive Dienes:

Require s-cis conformation s-trans s-cis Unreactive Dienes: Dienes are generally more reactive when substituted with
Require s-cis conformation s-trans s-cis Unreactive Dienes: Dienes are generally more reactive when substituted with

Dienes are generally more reactive when substituted with electron-donating groups, while dienophiles are more reactive with electron-withdrawing groups.

Stereoselectivity

EDG EDG: OR, OH, NR 2
EDG
EDG: OR, OH, NR 2
groups. Stereoselectivity EDG EDG: OR, OH, NR 2 cis CN CN NC trans Bicyclic Products CN

cis

CN

CN

NC trans
NC
trans

Bicyclic Products

CN

EDG: OR, OH, NR 2 cis CN CN NC trans Bicyclic Products CN + CN EWG

+

EDG: OR, OH, NR 2 cis CN CN NC trans Bicyclic Products CN + CN EWG
EDG: OR, OH, NR 2 cis CN CN NC trans Bicyclic Products CN + CN EWG

CN

OR, OH, NR 2 cis CN CN NC trans Bicyclic Products CN + CN EWG EWG:

EWG

EWG: CN, NO 2 , COR

trans Bicyclic Products CN + CN EWG EWG: CN, NO 2 , COR CN CN cis
trans Bicyclic Products CN + CN EWG EWG: CN, NO 2 , COR CN CN cis
CN CN
CN
CN

cis

CN CN
CN
CN

trans

endo (major) CN
endo
(major)
CN
+ H CN exo (minor) H
+
H
CN
exo
(minor)
H

Molecular Orbital Analysis

The Diels-Alder reaction relies on HOMO-LUMO interactions:

LUMO

Butadiene

HOMO

Ethene

Product

HOMO-LUMO interactions: LUMO Butadiene HOMO Ethene Product sigma bond This HOMO-LUMO interaction also works HOMO

sigma

bond

interactions: LUMO Butadiene HOMO Ethene Product sigma bond This HOMO-LUMO interaction also works HOMO Butadiene LUMO

This HOMO-LUMO interaction also works

HOMO

Butadiene

bond This HOMO-LUMO interaction also works HOMO Butadiene LUMO Ethene Example: Explain why this reaction is

LUMO

Ethene

Example: Explain why this reaction is thermally forbidden

Example: Explain why this reaction is thermally forbidden Energy no bond LUMO HOMO sigma bond H
Example: Explain why this reaction is thermally forbidden Energy no bond LUMO HOMO sigma bond H

Energy

no bond

LUMO why this reaction is thermally forbidden Energy no bond HOMO sigma bond H O M O
LUMO

HOMOwhy this reaction is thermally forbidden Energy no bond LUMO sigma bond H O M O why this reaction is thermally forbidden Energy no bond LUMO sigma bond H O M O

reaction is thermally forbidden Energy no bond LUMO HOMO sigma bond H O M O Ethene
reaction is thermally forbidden Energy no bond LUMO HOMO sigma bond H O M O Ethene

sigma

bond

HOMO

Ethene

Energy no bond LUMO HOMO sigma bond H O M O Ethene LUMO Ethene In general,

LUMO

Ethene

no bond LUMO HOMO sigma bond H O M O Ethene LUMO Ethene In general, concerted
no bond LUMO HOMO sigma bond H O M O Ethene LUMO Ethene In general, concerted

In general, concerted cycloaddition reactions involving 4n + 2 pi electrons are thermally allowed and photochemically f orbidden. Those involving 4n pi electrons are thermally f orbidden and photochemically allowed.

Reverse Diels-Alder General Mechanism: heat +
Reverse Diels-Alder
General Mechanism:
heat
+
Example:
Example:

heat

Diels-Alder General Mechanism: heat + Example: heat The Cope Rearrangement General Mechanism: R R heat
Diels-Alder General Mechanism: heat + Example: heat The Cope Rearrangement General Mechanism: R R heat
The Cope Rearrangement General Mechanism: R R heat
The Cope Rearrangement
General Mechanism:
R
R
heat

Examples:

H

Example: heat The Cope Rearrangement General Mechanism: R R heat Examples: H heat Transition State: R

heat

Example: heat The Cope Rearrangement General Mechanism: R R heat Examples: H heat Transition State: R

Transition State:

R

Example: heat The Cope Rearrangement General Mechanism: R R heat Examples: H heat Transition State: R
Example: heat The Cope Rearrangement General Mechanism: R R heat Examples: H heat Transition State: R
H O
H
O

heat

Example: heat The Cope Rearrangement General Mechanism: R R heat Examples: H heat Transition State: R
O
O

H