30.

Orbitals and Organic

Chemistry: Pericyclic
Reactions
Based on McMurry’s Organic Chemistry, 6th edition
©2003 Ronald Kluger
Department of Chemistry
University of Toronto
Pericyclic Reactions – What Are?
• Involves several simultaneous bond-making breaking
process with a cyclic transition state involving delocalized
electrons
• The combination of steps is called a concerted process
where intermediates are skipped

Based on McMurry, Organic Chemistry, Chapter

2
30, 6th edition, (c) 2003
 30.2 Molecular Orbitals and Pericyclic
Reactions
• If the symmetries of both reactant and product orbitals
match the reaction is said to be symmetry allowed under
the Woodward-Hoffmann Rules (these relate the
electronic configuration of reactants to the type of
pericyclic reaction and its stereochemical imperatives)
• If the symmetries of reactant and product orbitals do not
correlate, the reaction is symmetry-disallowed and there no
low energy concerted paths
• Fukui’s approach: we need to consider only the highest
occupied molecular orbital (HOMO) and the lowest
unoccupied molecular orbital (LUMO), called the frontier
orbitals
Based on McMurry, Organic Chemistry, Chapter
7
30, 6th edition, (c) 2003
Based on McMurry, Organic Chemistry, Chapter
9
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 Electrocyclic Reactions
• These are pericyclic processes that involves the
cyclization of a conjugated polyene
• One  bond is broken, the other  bonds change
position, a new σ bond is formed, and a cyclic
compound results
• Gives specific stereoisomeric outcomes related to
the stereochemistry and orbitals of the reactants

Based on McMurry, Organic Chemistry, Chapter

10
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Based on McMurry, Organic Chemistry, Chapter
11
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Example: Electrocyclic Interconversions With
Octatriene

Based on McMurry, Organic Chemistry, Chapter

12
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Example: Electrocyclic Interconversions with
Dimethylcyclobutene

Based on McMurry, Organic Chemistry, Chapter

13
30, 6th edition, (c) 2003
 The Signs on the Outermost Lobes
Must Match to Interact
• The lobes of like sign can be either on the same side or on opposite sides of
the molecule.
• For a bond to form, the outermost  lobes must rotate so that favorable
bonding interaction is achieved

Based on McMurry, Organic Chemistry, Chapter

14
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 Disrotatory Orbital Rotation
• If two lobes of like sign are on the same side of the molecule, the two orbitals
must rotate in opposite directions—one clockwise, and one counterclockwise
• Woodward called this a disrotatory (dis-roh-tate’-or-ee) opening or closure

Based on McMurry, Organic Chemistry, Chapter

15
30, 6th edition, (c) 2003
 Conrotatory Orbital Rotation
• If lobes of like sign are on opposite sides of the molecule: both orbitals
must rotate in the same direction, clockwise or counterclockwise
• Woodward called this motion conrotatory (con-roh-tate’-or-ee)

Based on McMurry, Organic Chemistry, Chapter

16
30, 6th edition, (c) 2003
 30.4 Stereochemistry of Thermal Electrocyclic
Reactions
•Determined by the symmetry of the
polyene HOMO
•For thermal reactions, ground-state
electronic configuration is used to identify
the HOMO
• For photochemical reactions excited-state
electronic configuration is used.

Based on McMurry, Organic Chemistry, Chapter

17
30, 6th edition, (c) 2003
•Polyenes with an even number of
electron pairs undergo thermal
electrocyclic reactions in a
conrotatory,
•odd number of electron pairs
undergo the same reactions in a
disrotatory sense.
Based on McMurry, Organic Chemistry, Chapter
18
30, 6th edition, (c) 2003
 Ring Closure of Conjugated Trienes
• Involves lobes of like sign on the same side of the molecule
and disrotatory ring closure

Based on McMurry, Organic Chemistry, Chapter

19
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Based on McMurry, Organic Chemistry, Chapter
20
30, 6th edition, (c) 2003
 30.5 Photochemical Electrocyclic
Reactions
• Irradiation of a polyene excites one electron from HOMO to
LUMO
• This causes the old LUMO to become the new HOMO, with
changed symmetry
• This changes the reaction stereochemistry (symmetries of
thermal and photochemical electrocylic reactions are always
opposite)

Based on McMurry, Organic Chemistry, Chapter

26
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Based on McMurry, Organic Chemistry, Chapter
27
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Rules for Electrocyclic Reactions

Based on McMurry, Organic Chemistry, Chapter

28
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Based on McMurry, Organic Chemistry, Chapter
37
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Based on McMurry, Organic Chemistry, Chapter
42
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 30.6 Cycloaddition Reactions
•Two unsaturated molecules add to one another,
yielding a cyclic product
•The Diels–Alder cycloaddition reaction is a
pericyclic process that takes place between a
diene (four  electrons) and a dienophile (two 
electrons) to yield a cyclohexene product
Stereospecific with respect to substituents

Based on McMurry, Organic Chemistry, Chapter

48
30, 6th edition, (c) 2003
Based on McMurry, Organic Chemistry, Chapter
49
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 Rules for Cylcoadditions - Suprafacial
Cycloadditions
• The terminal  lobes of the two reactants must have the correct
symmetry for bonding to occur
• Suprafacial cycloadditions take place when a bonding interaction
occurs between lobes on the same face of one reactant and
lobes on the same face of the other reactant

Based on McMurry, Organic Chemistry, Chapter

50
30, 6th edition, (c) 2003
Rules for Cylcoadditions - Antarafacial
Cycloadditions
• These take place when a bonding interaction occurs
between lobes on the same face of one reactant and lobes
on opposite faces of the other reactant (not possible unless
a large ring is formed)

Based on McMurry, Organic Chemistry, Chapter

51
30, 6th edition, (c) 2003
30.7 Stereochemistry of Cycloadditions
• HOMO of one reactant combines with LUMO of other
• Possible in thermal [4 +2] cycloaddition

Based on McMurry, Organic Chemistry, Chapter

52
30, 6th edition, (c) 2003
 [2+2] Cylcoadditions
• Only the excited-state HOMO of one alkene and the LUMO can combine by a
suprafacial pathway in the combination of two alkenes

Based on McMurry, Organic Chemistry, Chapter

53
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Formation of Four-Membered Rings
• Photochemical [2 + 2] cycloaddition reaction occurs
smoothly

Based on McMurry, Organic Chemistry, Chapter

54
30, 6th edition, (c) 2003
30.8 Sigmatropic Rearrangements
• A s -bonded substituent atom or group migrates
across a p electron system from one position to
another
• A s bond is broken in the reactant, the p bonds move,
and a new s bond is formed in the product

Based on McMurry, Organic Chemistry, Chapter

60
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Based on McMurry, Organic Chemistry, Chapter
61
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 Sigmatropic Notation
• Numbers in brackets refer to the two groups
connected by the s bond and designate the
positions in those groups to which migration occurs
• In a [1,5] sigmatropic rearrangement of a diene
migration occurs to position 1 of the H group (the
only possibility) and to position 5 of the pentadienyl
group
• In a [3,3] Claisen rearrangement migration occurs to
position 3 of the allyl group and also to position 3 of
the vinylic ether
Based on McMurry, Organic Chemistry, Chapter
62
30, 6th edition, (c) 2003
Sigmatropic Stereospecificity:
Suprafacial and Antarafacial
• Migration of a group across the same face of the  system is
a suprafacial rearrangement
• Migration of a group from one face of the  system to the
other face is called an antarafacial rearrangement

Based on McMurry, Organic Chemistry, Chapter

63
30, 6th edition, (c) 2003
Stereochemical Rules of Sigmatropic
Rearrangements
Electron Pairs Thermal Photochemical
Reaction Reaction
Even Number Antarafacial Suprafacial
Odd Number Suprafacial Antarafacial
H
H
H
H

ANTARA
SUPRA Based on McMurry, Organic Chemistry, Chapter
64
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30.10 A Summary of Rules for Pericyclic
Reactions

Based on McMurry, Organic Chemistry, Chapter

76
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