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
[Link]
[Link]
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
[Link]
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:
[Link]
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
[Link]
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