CHEM 6320 Fall 2005

B. Sigmatropic Rearrangements
1. Introduction
a. Sigmatropic rearrangements are reactions that involve a concerted
reorganization of electrons during which a group attached to a σ bond
migrates to the terminus of an adjacent π-electron system with a
simultaneous shift of the π electrons.
b. Sigmatropic rearrangements are labeled [i, j] where i represents the
number of atoms in the migrating fragment and j represents the number
of atoms in the π system directly involved in the bonding changes.
c. Topology of sigmatropic migration.
– Suprafacial (or supra) migration involves a process in which the
migrating group remains associated with the same face of the
conjugated π system throughout the process.
– Antarafacial (or antara) migration involves a process in which
the migrating group moves to the opposite face of the π system
during the migration.
d. Examples
a c a c a c a H
H H H c
b d b d b d b d
1,3-suprafacial shift of hydrogen 1,3-antarafacial shift of hydrogen

R R
R R
1,3-shift of alkyl group 1,5-shift of alkyl group

O O

3,3-sigmatropic rearrangement of 1,5-hexadiene 3,3-sigmatropic rearrangement of allyl vinyl ether

(Cope rearrangement) (oxi-Cope rearrangement)

CH3 C H2 CH2 H3C CH2R C H2 CH2 RCH2

1,7-sigmatropic shift of hydrogen 1,7-sigmatropic shift of alkyl group

+ _ + _
R S O R S O R2N O R2N O
2,3-sigmatropic rearrangement of allyl sulfoxide 2,3-sigmatropic rearrangement of amine oxide

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2. Classification of Sigmatropic Hydrogen/Alkyl Shifts

suprafacial 1,3 1,3 suprafacial retention 1,3 suprafacial inversion

Hückel system Hückel system Möbius system
4 electrons 4 electrons 4 electrons

suprafacial 1,5 1,5 suprafacial retention 1,5 suprafacial inversion

Hückel system Hückel system Möbius system
6 electrons 6 electrons 6 electrons

antarafacial 1,7 suprafacial 1,7

Möbius system Hückel system
8 electrons 8electrons

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3. Selection Rules for Sigmatropic Shifts of Order [i, j]

Order [1, j] 1+ j supra/ret* supra/inv* antara/ret* antara/inv*
4n forbidden allowed allowed forbidden
4n + 2 allowed forbidden forbidden allowed
Order [i, j] i + j supra/supra supra/antara antara/antara
4n forbidden allowed forbidden
4n + 2 allowed forbidden allowed
(*ret = retention, inv = inversion)
4. Examples
a. 1,3-alkyl shift occurs thermally with inversion of configuration of
migrating carbon
H H
H D H D
H H
∆
H H
OAc OAc

H H
D H OAc
H H
H H D
H D H
OAc OAc H
product if retention product if inversion
(not observed) (observed)
– This reaction is not possible for hydrogen.
b. 1,5-alkyl shift occurs thermally with retention of configuration of
migrating carbon
Me H Me H Me H Me

Me H Me H Me H Me

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c. Cope rearrangement (3,3-sigmatropy on 1,5-diene)

CN ∆ CN

COOEt COOEt
– The product is stabilized because it allows conjugation.
– Reaction proceeds usually through chair-like transition state.
(Boat-like transition state is less stable by about 6 kcal/mol.)
Me Me
Ph Ph

Me Me
E (major)
Ph Ph

Me Me
Me Me
Z (minor)
– Both transformations are electronically allowed.
– Chirality in reactant is translated into the product. (This is a
general feature of sigmatropic shifts.)
d. Degenerate rearrangement
H H
fast at high T

H H
– The molecule (homotropilidene) transforms into itself.
– At low temperature, the transformation is slow so the 13C NMR
gives five signals (five different carbons).
– At high temperature, the transformation is fast so the 13C NMR
gives three signals (three different carbons).
– Another example is bullvalene:

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C. Cycloaddition Reactions
1. Diels-Alder Reaction
a. Cycloaddition reactions involve two molecules as reactants.
b. Diels-Alder reaction, also called the [4π + 2π] cycloaddition (or 4 + 2
cycloaddition), is the addition of an alkene (or dienophile) to a diene.
c. Diels-Alder reaction involves 6 electrons so the transition state has a
Hückel topology. The reaction is stereospecific syn (suprafacial) with
respect to both diene and alkene.
d. Correlation diagram for [4π + 2π] cycloaddition
– Define a symmetry element preserved
R → ‡ → P. In this case, this is a plane of
symmetry.
– Assign all reacting orbitals as symmetric
H H
(S) or antisymmetric (A) with respect to HH
the symmetry element.
– Draw the correlation diagram and identify
correlations between the reactant and H H
product orbitals H H
– Fill the orbitals with electrons and decide
if the reaction is allowed.

– Same arguments show that 2 + 2 cycloaddition is forbidden.

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2. Selection Rules for m + n Cycloadditions

m+n supra/supra supra/antara antara/antara
4n forbidden allowed forbidden
4n + 2 allowed forbidden allowed
3. Stereochemistry of Diels-Alder Reaction
a. Alder Rule
– If two isomeric adducts are possible, the one that has an
unsaturated substituent(s) on the alkene oriented toward the
newly formed cyclohexene double bond is the preferred product.
– In other words, endo stereoisomer is preferred over exo
stereoisomer.
R R R R
X H X
X X
+
H
R endo addition R R R

R R R R
X H X
X X
+
H
R exo addition R R R
– Example:
H
O
endo H
O product O

+ O O
O
exo
O product O
H
O
H

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b. Regioselectivity of the Diels-Alder reaction

– It gives the preferred (major) product of a Diels –Alder reaction
when both diene and dienophile are not symmetric (i.e., are
substituted).
– The reactivity is enlarged when the substituent on one reactant is
electron-withdrawing group (EWG) while the substituent on the
other reactant is electron-releasing group (ERG).
– The four possibilities and the major products are given below:

ERG ERG
EWG EWG
type A:

ERG ERG
type B:
EWG EWG

EWG EWG
ERG ERG
type C:

EWG EWG
type D:
ERG ERG

– The preferred orientation is governed by matching largest

coefficients on interacting frontier orbitals (HOMO of one
molecule and LUMO of the other molecule).

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D. Problems and Exercises

1. Show, by constructing a correlation diagram, whether each of the following

disrotatory cyclizations is symmetry allowed:
a. pentadienyl cation to cyclopentenyl cation
b. pentadienyl anion to cyclopentenyl anion

2. Which of the following reactions are allowed according to the orbital

symmetry conservation rules? Explain.
H H

COOCH3 ∆ H
H COOCH3
COOCH3
a. COOCH3

. ∆
.
b.

H
O O
H
O O
c.

CH3
CH3
CH2OSi(CH3)3 ∆
CH3CH2
H3C
d. OSi(CH3)3

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3. Suggest a mechanism by which each transformation could occur. (More

than one step can be involved.)
HO CH3
CH3CH C CH O
100°C
a. CH3

370°C

b.

4. Predict the regiochemistry and stereochemistry of the following

cycloadditions reactions and indicate the basis of your prediction.

O
CH3 H
+ O
H CH CH2
a. O

CH3O2CNH H
+ H2C CHCOOCH3
b. H CH CH2

CH3 H
H
+ N
H
c. H CN

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5. Give the structure, including stereochemistry, of the products expected for

the following reaction.
CN
+
a.

+ Ph2C C O
b.

c.

OSiR3
heat

d. CHO

+ CH3OOC C C COOCH3
e.

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