Chapter 30

Orbitals and organic chemistry: Pericyclic reactions

Intended learning outcomes:

1. To understand the mechanism and stereochemistry of the three major
groups of pericyclic reactions and understand whether they will proceed
under certain conditions, using molecular orbitals:
--electrocyclic reactions: disrotatory/conrotatory; thermal/photochemical
--cycloaddition reaction: suprafacial/antarafacial; thermal/photochemical
--sigmatropic rearrangement: hydride shift and Cope/Claisen reactions
2. To be able to use Diels-Alder reactions and Cope and Claisen
rearrangment in organic synthesis.
The Third Type of Organic Reactions

1. Radical reactions: symmetric bond breaking or formation

2. Polar reactions: asymmetric bond breaking or formation

3. Pericyclic reactions:
--Neither radical nor ionic reactions
--Simultaneous breaking and formation of multiple bonds (>2)
--Not stepwise, but concerted (single TS, no intermediate)
Claisen Rearrangement

H2 H2
C C H2C H H 2C
O CH O CH O CH O CH

CH2 CH2 CH2 CH2

Transition state Intermediate

https://www.youtube.com/watch?v=KI8Cb9LXGFk
https://www.youtube.com/watch?v=WgbXMisZdqw
Diels-Alder Reactions
Molecular Orbitals: Conjugated and Nonconjugated dienes

LUMO
Ethylene

 HOMO

HOMO: highest occupied molecular orbital

LUMO: lowest unoccupied molecular orbital

LUMO
1, 3-butadiene
 HOMO


https://www.youtube.com/watch?v=Mky1uSLdpSE
Molecular Orbitals: Only the Node Number Counts

LUMO
1,3,5-
hexatriene
 HOMO




Pericyclic Reactions: Symmetry Rules

Robert B. Woodward Roald Hoffman Kenichi Fukui

(1917-1979) (1937-) (1918-1998)

R. B. Woodward and R. Hoffman:

Symmetries of the reactant and product MOs must be the same.
--the lobes of reactant MOs must be of the right sign for bonding in the TS.
--symmetry-allowed and symmetry-forbidden reactions
K. Fukui:
Only LUMO and HOMO orbitals need to be considered.
--develop the frontier orbital theory for all chemical reactions.

Nobel Prize 1981

Electrocyclic Reactions: Cyclization of Conjugated Polyenes
Pericyclic reactions involving cyclization of conjugated polyenes.

How do these happen?

OR

Stereochemistry?
Thermal Electrocyclic Reactions: 1,3-Butadiene

LUMO

 HOMO



HOMO
Stereochemistry: Thermal Cyclization of 1,3-Butadiene

Woodward and Hoffman rule:

The lobes of reactant MOs must be of the right sign for bonding.

Symmetry-allowed
Photochemical Electrocyclic Reactions: Excited 1,3-Butadiene

HOMO

Ground state Excited state

Thermal reaction Photochemical reaction

HOMO
Stereochemistry: Photochemical Cyclization of 1,3-Butadiene

Symmetry-allowed
Thermal Electrocyclic Reactions: 1,3,5-Hexatriene

LUMO

 HOMO




Thermal Electrocyclic Reactions: 1,3,5-Hexatriene

HOMO

Symmetry-allowed
Photochemical Electrocyclic Reactions of 1,3,5-Hexatriene

HOMO
Photochemical Electrocyclic Reaction of 1,3,5-Hexatriene

HOMO

Symmetry-allowed
Electrocyclic Reactions: Polyenes

Diene: 2 x
Tetraene: 4 x Ground state: conrotatory
Thermal electrocyclic reactions
Hexaene: 6 x
………

Triene: 3 x
Ground state: disrotatory
Pentaene: 5 x Thermal electrocyclic reactions
Heptaene: 7 x
………
Cycloaddition reactions: Diels-Alder (4+2) reactions

Viewed as: one reactant donates 2e to the other reactant

Donor uses the 2e in HOMO, whereas the acceptor 2e in LUMO

LUMO HOMO
of diene of diene

HOMO LUMO
of dienophile of dienophile

Suprafacial cycloaddition:
both reactants use lobes on the same side of their  orbital systems
Cycloaddition Reactions: Diels-Alder (4+2) Reactions

Thermal:

https://www.youtube.com/watch?v=7WCSY_4EAkA
Photochemical:
Symmetry allowed, but
LUMO geometric constraints often
of dienophile make antarafacial reactions
difficult.

HOMO of diene Example: (4+2)

photochemical reactions
NOT observed.

Antarafacial cycloaddition:
One reactant use lobes on the same side of its  orbital system; the other reactant use
lobes on different sides of its  orbital system.
Cycloaddition Reactions: (2+2) Reactions

Thermal conditions Photochemical conditions

Successful photochemical (2+2) reactions

Cycloaddition reactions: General rules

Stereochemical restriction:

(2+2) = (2 + 6) = (2 + 10) = (2 + 14) = ……..

= (6 + 6) = (6 + 10) = (6 + 14) = ……..= even number of  bonds

(4+2) = (4 + 6) = (4 + 10) = (4 + 14) = ……..

= (8 + 6) = (8 + 10) = (8 + 14) = ……..= odd number of  bonds
Questions
What type of reactions? Suprafacial or antarafacial?
Sigmatropic Rearrangement

A -bonded atom or group migrates across a -system

from one position to another.

• [1,5] hydride shift: [1,5] sigmatropic rearrangement

• [3,3] sigmatropic rearrangement: Claisen rearrangment

Sigmatropic Rearrangement: [1,5] Hydride Shift

3*

2* [1,5] hydride shift: suprafacial, easy to happen

1*

[1,3] hydride shift: antarafacial, no reaction.

 3 HOMO

 2

 1
Sigmatropic Rearrangement: [1,7] Hydride Shift
[1,7] hydride shift: antarafacial, can happen
Sigmatropic Rearrangement: Cope Rearrangement

[3,3] rearrangements: suprafacial, Cope and Claisen rearrangement

https://www.youtube.com/watch?v=grj5Pe7jwPE
Sigmatropic Rearrangement: Examples

Claisen
rearrangement
Sigmatropic Rearrangement: Examples

Claisen rearrangement

Cope rearrangement
Sigmatropic Rearrangements in Biology

Tyrosine

Vitamin D
Summary for Pericyclic Reactions

1. Electrocyclic reactions: stereochemistry for ground and excited states

2. Cycloaddition reactions: stereochemistry for ground and excited states
3. Sigmatropic rearrangements: hydride shift, Cope and Claisen
rearrangements.
Practice Problems

7th Ed.
30.13, 30.14, 30.15, 30.16, 30.17, 30.18,
30.20, 30.22, 30.23, 30.24, 30.26, 30.27,
30.28, 30.31, 30.32, 30.33, 30.35, 30.36,
30.38, 30.39, 30.40

8th Ed.
30.13, 30.28, 30.17, 30.14, 30.18, 30.15,
30.19, 30.32, 30.30, 30.26, 30.31, 30.27,
30.24, 30.23, 30.26, 30.37, 30.34, 30.33,
30.39, 30.38, 30.41