SBM CDT Modern Pericyclics

Pericyclic Reactions 1
Pericyclic Reactions
The Woodward Hoffmann Approach
HOMO diene
O
O π4s 6 electrons
no nodes
Hückel
O
(4q + 2)s = 1 π2s allowed ✓
O (4r)a = 0
Total = 1
O odd ✓ LUMO dienophile
allowed construcZve overlap ✓
Full handout for 3rd year course at h3p://burton.chem.ox.ac.uk/teaching.html
︎ ︎Pericyclic Reac+ons, Oxford Chemistry Primer no. 67; Ian Fleming

︎ Organic Chemistry Jonathan Clayden, Nick Greeves, Stuart Warren, Peter Wothers
Advanced Organic Chemistry: Reac+ons, Mechanisms and Structures; Jerry March
Fron+er Orbitals and Organic Chemical Reac+ons; Ian Fleming
Molecular Orbitals & Organic Chemical Reac+ons; Ian Fleming
Modern Physical Organic Chemistry; Eric Anslyn and Dennis Docherty

jonathan.burton@chem.ox.ac.uk
Pericyclic Reac@ons

Pericyclic reacZons – ReacZons in which all first-‐order changes in bonding relaZonships take
place in concert on a closed curve. R. B. Woodward and R. Hoffmann 1969.

i.e. the reacZons have cyclic transiZon states in which all bond-‐forming and bond-‐
breaking take place in a concerted manner without the formaZon of an intermediate.
Pericyclic reacZons involve a transiZon state with a cyclic array of interacZng orbitals; a
reorganisaZon of σ and π-‐bonds occurs within this cyclic array.
Originally termed ‘ no mechanism reacZons’ – they could not be explained by standard
nucleophile/electrophile mechanisms.
O O
H H
O O
O O
No absolute sense in which the electrons flow from one component to another;
however, someZmes it is more sensible to push the arrows in only one direcZon.
Here curly arrows are used to show which bonds are being made/broken rather than
the direcZon of flow of electrons.

Four classes.

CycloaddiZons -‐ Two components come together to form two new σ-‐bonds at the ends of both components and
joining them together to form a ring. Bimolecular form/break a ring.
Cheletropic reacZons are a sub-‐class of cycloaddiZon reacZons in which the two σ – bonds are made or broken to the same atom.
O
Me O Me O
N N + CO
Me Me
Electrocyclic ReacZons – Unimolecular reacZons characterised by the forma@on of a ring from an open chain
conjugated system with a σ-‐bond forming across the ends of the conjugated system. Unimolecular form/break
a ring.
Me Me Me
heat heat
Me
Me Me Me Me
Sigmatropic rearrangements – Unimolecular isomerisa@ons which formally involve the overall

movement of a σ-‐bond from one posiZon to another. Unimolecular do not form/break a ring.
1
3 2 1 H 1 H
[3,3] 5 [1,5]
4 2
3 3
2 1
Group transfer – appear to be a mix of a sigmatropic rearrangement and a cycloaddiZon. They are
bimolecular and so are not sigmatropic rearrangements, and no ring is formed so they are not cycloaddiZons.
Biomolecular do not form/break a ring.
O O
H N N N N
H
H H
O O H H
O O
CorrelaZon Diagrams

During a pericyclic reacZon the orbitals of the starZng material are smoothly converted into the orbitals of the
product.

This means that the symmetry of the orbitals with respect to any symmetry operaZons of the molecule must be
conserved in moving from the starZng material(s) to product – this is the ‘ConservaZon of Orbital Symmetry’, which
is readily depicted in an ‘orbital correlaZon diagram’
Draw bare bones of reacZon.
IdenZfy orbitals undergoing change.
Draw sensible approach of substrates.

σ σ
IdenZfy symmetry elements maintained during reacZon.
A σ4
Rank orbitals approximately by energy. A
ψ4 S
σ3
Classify each orbital with respect to the symmetry
element(s) conserved during reacZon. π* A A π*
Construct orbital correlaZon diagram connecZng orbitals

of starZng materials with those closest in energy and of the ψ3 S
same symmetry in the product.
ψ2 A
In the Diels-‐Alder reacZon a plane of symmetry,
perpendicular to the molecular planes of both the diene
and dienophile and passing through the double bond of the π S S π
dienophile and the central single bond of the diene.
S A
ψ1
In the orbital correlaZon diagram of the Diels-‐ Alder σ2
reacZon all interacZng bonding orbitals in the diene/ S
dienophile are correlated with new bonding orbitals in the σ1
product. The reacZon is thermally allowed.
CorrelaZon diagram for electrocyclic reacZons

Me
Z,E : E,E 20,000:1
Me
Me Longuet-‐Higgins & Abrahamson, J. Am. Chem. Soc., 1965, 87, 2045.
Me
There are two modes of opening – conrotatory or disrotatory

Conrotatory – rota+on around the axes of the σ-‐bonds (doSed lines ) occurs in the same direc+on -‐
throughout this process the molecule retains a C2-‐axis which passes through the plane of the molecule and the
breaking σ bond.
C2
plan view
Disrotatory – rota+on around the axes of the σ-‐bonds (doSed lines) occurs in opposite direc+ons –
throughout this process the molecule retains a plane of symmetry which is perpendicular to the plane of
the molecule and passes through the breaking σ-‐bond
σ
plan view
CorrelaZon diagram for electrocyclic reacZons.

IdenZfy orbitals undergoing change (curly arrows) – σ and π. molecular)
The orbitals undergoing change are either symmetric or anZsymmetric with respect to the plane
symmetry elements preserved during the reacZon.
Rank orbitals approximately by energy. C2 σ
Label orbitals as ‘S’ or ‘A’.
Construct orbital correlaZon diagram connecZng orbitals of starZng materials
with those closest in energy and of the same symmetry in the product.
R R R
R conrotatory disrotatory
R R
under C2 under σ
ψ4 R R R ψ4
R R
σ* R
ψ3 R R R ψ3
R
R π* R
ψ2 R R R ψ2
R
R π R
ψ1 R R R ψ1
R
R σ R
R R R
R conrotatory disrotatory molecular)
R R plane
under C2 under σ
S A A A C2 σ
ψ4 R R R ψ4
R R
σ* R
ψ3 A S A S ψ3
R R R
R
R π* R
ψ2 S A S A ψ2
R R R
R
R π R
ψ1 R
A S S S R R ψ1
R
R σ R
In the conrotatory mode, all ground state bonding orbitals in cyclobutene (σ2π2) correlate with ground state
bonding orbitals in butadiene (ψ12ψ22) – the conrotatory opening of butadiene is thermally allowed (favoured).
In the disrotatory mode, the ground state bonding orbitals in cyclobutene (σ2π2) correlate with a doubly excited
state of butadiene (ψ12ψ32) – the disrotatory opening of butadiene is thermally forbidden (disfavoured).
The photochemical ring closure of butadiene to give cyclobutene is disrotatory.
The 1st excited sate of butadiene is ψ12ψ21ψ31 which correlates smoothly with the 1st
hν
excited sate of cyclobutene (σ2π1π*1); under conrotatory ring closure ψ12ψ21ψ31
correlates with a much high energy state in cyclobutene (σ1π2σ*1).
CorrelaZon diagrams can be disZlled into a simple rule for predicZng which pericyclic reacZons are
“allowed”.

The Woodward-‐Hoffmann Rules:
A ground state pericyclic reacZon is symmetry allowed when the total number of (4q + 2)s and (4r)a
components is odd (q and r must be integers).
A pericyclic change in the first electronically excited state (i.e. a photochemical reacZon) is symmetry-‐
allowed when the total number of (4q + 2)s and (4r)a components is even.
We will use the Diels-‐Alder reacZon to exemplify the applicaZon of the Woodward-‐Hoffmann rules.
Draw a ‘curly arrow’ mechanism to idenZfy the components.
For the Diels-‐Alder reacZon these are 4π (diene) and 2π (dienophile).
Draw a convincing 3-‐D orbital diagram to show the overlap of the components.
Label the components as supra or antarafacial.
Sum the components according to the Woodward-‐Hoffmann rule.

Draw a ‘curly arrow’ mechanism – this generally allows idenZficaZon of the components.
For the Diels-‐Alder reacZon these are 4π (diene) and 2π (dienophile),
Draw a convincing 3-‐D orbital diagram to show the overlap of the components.
Label the components as supra or antarafacial. Here the diene is being used in a suprafacial manner –
the two new bonds are being formed on the same face of the diene.
The alkene is also being used in a suprafacial manner being used in a suprafacial manner
Sum the components according to the Woodward-‐Hoffmann rule
π2s
(4q + 2)s = 1 (4q + 2)s = 3
(4r)a = 0 (4r)a = 0
π4s Total = 1 Total = 3
odd ✓ odd ✓
allowed
π2s
allowed
π2s π2s
π2a
π2a
(4q + 2)s = 1 (4q + 2)s = 2
(4r)a = 0 (4r)a = 0
H H
Total = 1 X Total = 2
even ✗
odd ✓
π2a allowed π2s forbidden
π2s π2s
Generally simplest to maximise suprafacial components and not subdivide conjugated systems.
[2 + 2] cycloaddiZons
Draw a ‘curly arrow’ mechanism to idenZfy the components – 2π, 2π
Draw a convincing 3-‐D orbital diagram to show the overlap of the components O O
Label the components as supra or antarafacial. heat
Sum the components according to the Woodward-‐Hoffmann rule
O X O
O O
π2s
π2a (4q + 2)s = 1
π2s (4q + 2)s = 2 (4r)a = 0
(4r)a = 0 Total = 1
Total = 2 odd ✓
π2s
even ✗
π2s
allowed
forbidden (thermally)
(thermally) but geometrically
π2a unreasonable,
(4q + 2)s = 2
(4r)a = 0 therefore does not
Total = 2 occur
even ✓
allowed –
photochemically
Woodward-‐Hoffmann rule gives you the symmetry allowed orbital overlap but you have to decide whether
the overlap you have drawn is geometrically reasonable.
Nomenclature for suprafacial and antarafacial components.

Suprafacial and antarafacial refer to modes of bond formaZon that are respecZvely on the same face or on
opposite faces of a molecular component.
C H
σ-‐suprafacial
π-‐suprafacial π-‐antarafacial
σ-‐antarafacial
σ-‐suprafacial σ-‐antarafacial ω-‐suprafacial ω-‐antarafacial

Woodward-‐Hoffmann approach for thermal electrocyclic reacZons Me
Draw a ‘curly arrow’ mechanism to idenZfy the components – Me

these are 2π (alkene) and 2σ (single bond) Me
Me
Draw a convincing 3-‐D orbital diagram to show the overlap of the components
Sum the components according to the Woodward-‐Hoffmann rule.
π2s
π2a (4q + 2)s = 1 (4q + 2)s = 1
Me Me (4r)a = 0 (4r)a = 0
Me Me
Total = 1 Total = 1
odd ✓ odd ✓
allowed allowed
(conrotatory) σ2a (conrotatory)
H H
σ2s
H H
π2s
(4q + 2)s = 2
Me Me (4r)a = 0
Total = 2
even ✗ X Me
Me
forbidden
H σ2s H disrotatory
Thermal ring opening of cyclobutene is conrotatory. Thermal disrotatory opening is symmetry forbidden.
Woodward-‐Hoffmann approach for sigmatropic rearrangements

Draw a ‘curly arrow’ mechanism to idenZfy the components – 2π, 2σ, 2π
Label the components as supra or antarafacial. Me Me
O O
Sum the components according to the Woodward-‐Hoffmann rule. Me Me
σ2s
O
π2s O
σ2s
O π2s
σ2s
Me
π2s
Me Me
Me
π2s (4q + 2)s = 3 (4q + 2)s = 3
π2s π2s (4r)a = 0
(4r)a = 0 Me
Me Total = 3
Total = 3
odd ✓ odd ✓
allowed allowed
Claisen rearrangement via chair TS is allowed. Claisen rearrangement via boat TS is allowed.
Woodward-‐Hoffmann rule does not tell us that the chair TS is lower in energy than the boat TS. You need to use your
chemical knowledge/intuiZon to decide that a chair is generally lower in energy than the corresponding boat and that it
is generally more favourable to have equatorial subsZtuents than axial subsZtuents on a chair.
Woodward-‐Hoffmann approach for sigmatropic rearrangements and group transfer

Draw a ‘curly arrow’ mechanism to idenZfy the components
Sum the components according to the Woodward-‐Hoffmann rule. O
O
H H
O O
S O
O Ph SPh O
O
π2s
O ω2s
O
(4q + 2)s = 3 (4q + 2)s = 3
Ph S Ph S (4r)a = 0 (4r)a = 0
Total = 3 Total = 3
π2s
H
π2s
H
σ2s
odd ✓
σ2s
odd ✓
allowed allowed
[2,3]-‐sigmatropic rearrangement via envelope TS. ene-‐reacZon (group transfer) via envelope TS.
For thermal cycloaddiZons and group transfers:
If the total number of electrons is (4n + 2) both components can be used in a suprafacial manner.
If the total number of electrons is (4n) one of the components is suprafacial and the other antarafacial.
For electrocyclic reacZons:
Thermal electrocyclic processes will be conrotatory if the total number of electrons is 4n and disrotatory if the
total number of electrons is (4n +2).
FronZer Molecular Orbital approach – revision

‘As two molecules approach each other, three major forces operate:
(i) The occupied orbitals of one repel the occupied orbitals of the other.
(ii) Any posiZve charge on one avracts any negaZve charge on the other (and repels any posiZve)
(iii) The occupied orbitals (especially the HOMOs) of each interact with the unoccupied orbitals (especially the
LUMOs) of the other, causing an avracZon between the molecules.’ (from Fleming, Molecular Orbitals and Organic Chemical
ReacZons)
FronZer Molecular Orbital considers the interacZon of the Highest Occupied Molecular Orbital (HOMO) and the
Lowest Unoccupied Molecular Orbital (LUMO) to be of overriding importance.
LUMOa empty MOa empty MOb
thermal reacZon
HOMOb
filled MOa filled MOb
For photochemical reacZons one molecule is in the excited state
ψ4 ψ4
ψ3 HSOMO • ψ3 LUMO excited state a ground state b
hν •
• HSOMOa unoccupied MO ψ3
ψ2 • • LSOMO • • • ψ2 HOMO
ψ • • • • • • • • ψ
1 1 LSOMOa occupied MO ψ2
a a* b
ψ12ψ22 ψ12ψ21ψ31
The FMO approach

To apply the FMO method one has to assign a single HOMO and a single LUMO to the reacZon components and see
how they interact.

The FMO approach is simple to apply to reacZons with two components (e.g. cycloaddiZons, electrocyclic ring
opening) but its applicaZon to sigmatropic rearrangements and group transfer reacZons is somewhat contrived.
Assign a single HOMO and a single LUMO to the reacZon
Check to see if there is construcZve overlap between the orbitals
HOMO diene LUMO diene
(4q + 2)s = 1
π4s
(4r)a = 0
Total = 1
odd ✓
π2s allowed
LUMO dienophile HOMO dienophile
construcZve overlap ✓ construcZve overlap ✓

The FMO approach Me

Draw a ‘curly arrow’ mechanism to idenZfy the components heat Me
Me
Me
LUMO alkene LUMO alkene
Me H Me H
Me Me
Me
Me
H Me H Me
HOMO sigma construcZve overlap HOMO sigma construcZve overlap ✓
π2s
HOMO alkene
Me H
(4q + 2)s = 1
Me H (4r)a = 0
Total = 3
odd ✓
allowed
σ2a
H Me
H
LUMO sigma
Me (conrotatory)

construcZve overlap ✓
The preference of one conrotatory (or disrotatory) mode is termed torqueoselec+vity (more later).
The FMO approach

hν
Assign a single HSOMO and a single LUMO to the reacZon, (or a single LSOMO and HOMO) –
note a HSOMO has the same phases as the ‘LUMO’ and a LSOMO has the same phases as the HOMO)
HOMO LSOMO
alkene alkene Me Me
hν
Me Me
construcZve overlap ✓ H H
(disrotatory)
π4s
(4q + 2)s = 0
(4r)a = 0
Total = 0
even ✓
allowed
Me Me photochemically
(disrotatory)

The FMO approach

Me Me
O O
Me Me
HOMO ‘π + σ’ LUMO ‘π + σ’
O
O O O π2s
σ2s
Me
Me Me Me
π2s
Me
Me Me Me
LUMO alkene HOMO alkene (4q + 2)s = 1
(4r)a = 0
construcZve overlap ✓ construcZve overlap ✓ Total = 3
odd ✓
allowed
ψ2 ψ3
HOMO butadiene LUMO butadiene
The FMO approach

S O
Assign a single HOMO and a single LUMO to the reacZon O Ph SPh
O
HOMO ω
O LUMO, σ + ω
O
Ph S Ph S
Ph S
HOMO alkene
LUMO, alkene + σ
construcZve overlap ✓ construcZve overlap ✓
ψ3 ψ3
ω2s
LUMO butadiene LUMO 4e-‐ allyl O
Ph S (4q + 2)s = 3
π2s (4r)a = 0
σ2s Total = 3
odd ✓
allowed
Pericyclic reacZon summary:
Four classes:
CycloaddiZons (chelotropic reacZons); Electrocyclic reacZons; Sigmatropic rearrangements; Group transfer.
Woodward-‐Hoffmann rules:
A ground state pericyclic reacZon is symmetry allowed when the total number of (4q + 2)s and (4r)a
components is odd (q and r must be integers).
A pericyclic change in the first electronically excited state (i.e. a photochemical reacZon) is symmetry-‐
allowed when the total number of (4q + 2)s and (4r)a components is even.
For thermal cycloaddiZons and group transfers:

If the total number of electrons is (4n + 2) both components can be used in a
suprafacial manner.
If the total number of electrons is (4n) one of the components is suprafacial and the
other antarafacial.
For electrocyclic reacZons:
Thermal electrocyclic processes will be conrotatory if the total number of electrons is
4n and disrotatory if the total number of electrons is (4n +2).

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Pericyclic Reactions 1

Full handout for 3rd year course at h3p://burton.chem.ox.ac.uk/teaching.html

︎ ︎Pericyclic Reac+ons, Oxford Chemistry Primer no. 67; Ian Fleming

Sigmatropic rearrangements – Unimolecular isomerisa@ons which formally involve the overall

Draw bare bones of reacZon.

IdenZfy orbitals undergoing change.

Draw sensible approach of substrates.

Construct orbital correlaZon diagram connecZng orbitals

CorrelaZon diagram for electrocyclic reacZons

There are two modes of opening – conrotatory or disrotatory

CorrelaZon diagram for electrocyclic reacZons.

Draw a ‘curly arrow’ mechanism to idenZfy the components.

Label the components as supra or antarafacial.

Sum the components according to the Woodward-­‐Hoﬀmann rule.

Nomenclature for suprafacial and antarafacial components.

σ-­‐suprafacial σ-­‐antarafacial ω-­‐suprafacial ω-­‐antarafacial

Woodward-­‐Hoﬀmann approach for thermal electrocyclic reacZons Me

Draw a ‘curly arrow’ mechanism to idenZfy the components – Me

Woodward-­‐Hoﬀmann approach for sigmatropic rearrangements

Woodward-­‐Hoﬀmann approach for sigmatropic rearrangements and group transfer

FronZer Molecular Orbital approach – revision

LUMOa empty MOa empty MOb

The FMO approach

LUMO dienophile HOMO dienophile

construcZve overlap ✓ construcZve overlap ✓

The FMO approach Me

The FMO approach

The FMO approach

The FMO approach

Pericyclic reacZon summary:

For thermal cycloaddiZons and group transfers:

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Sum the components according to the Woodward-‐Hoﬀmann rule.

σ-‐suprafacial σ-‐antarafacial ω-‐suprafacial ω-‐antarafacial

Woodward-‐Hoﬀmann approach for thermal electrocyclic reacZons Me

Woodward-‐Hoﬀmann approach for sigmatropic rearrangements

Woodward-‐Hoﬀmann approach for sigmatropic rearrangements and group transfer