942 CHAPTER 36 

  PARTICIPATION, REARRANGEMENT, AND FRAGMENTATION

the LUMO must clearly be the empty p orbital of the cation, and the HOMO is the C–C σ
bond, which is about to break.

H
LUMO: empty p orbital H H H
H
H H
H H
Me HOMO:
filled σ Me H
H H orbital

The methyl group can slide smoothly from one orbital to another—there are bonding inter-
actions all the way. The next step, migration of H, is just the same—except that the HOMO is
now a C–H σ bond. The methyl migration is thermodynamically unfavourable as it trans-
forms a secondary cation into an unstable primary cation but the hydride migration puts that
right as it gives a stable tertiary cation. The whole reaction is under thermodynamic control.

HOMO: H LUMO: Me H
filled σ orbital empty p orbital
H Me
Me
Me H H H

Wagner–Meerwein rearrangements
Carbocation rearrangements involving migration of H or alkyl groups don’t just happen in
NMR machines. They happen during normal reactions too. For example, acid-catalysed
dehydration of the natural product camphenilol gives the alkene santene (a key component
of the fragrance of sandalwood oil) in a reaction involving migration of a methyl group.

Me H+ Me
camphenilol santene
Me
OH Me

The mechanism shows why the rearrangement happens: the fi rst-formed cation cannot
eliminate H+ in an E1 reaction because loss of the only available proton would give a very
strained bridgehead alkene (make a model and see!).

Me Me Me
×
Me Me Me
H this alkene would
OH2
this proton cannot be lost be very strained

However, migration of a methyl group both stabilizes the cation—it becomes tertiary
The impossibility of instead of secondary—and allows E1 elimination of H+ to take place to give a stable alkene.
bridgehead alkenes (Bredt’s rule)
was discussed in Chapter 17, tertiary
p. 389. methyl
carbocation
Me Me E1 elimination Me
migration
H
Me
secondary
Interactive mechanism for carbocation Me Me
Wagner–Meerwin rearrangements
The migration of an alkyl group to a cationic centre is known as a Wagner–Meerwein
rearrangement or Wagner–Meerwein shift, and this migration is, of course, a synthetic manifesta-
tion of the rearrangement we have just been looking at in NMR spectra. Wagner–Meerwein shifts
have been studied extensively in the class of natural products to which both of these natural
products belong—terpenes. For the moment, though, we will just illustrate this type of reaction
with one more example—another acid-catalysed dehydration, of isoborneol to give camphene.
 C A R B O C AT I O N S R E A D I LY R E A R R A N G E 943

isoborneol H+ camphene

HO

This one seems much more complicated—but, in fact, only one alkyl migration is involved.
1
To see what has happened, remember the ‘top tip’—number the carbons. You can number the 2
7 3
starting material any way you choose—we’ve started with the gem-dimethyl group because it HO 5
will be easy to spot in the product. The numbers just follow round the ring, with C8 being the 6 4
8
methyl group attached to C5.
Now for the hard bit—we need to work out which carbon in the starting material becomes
which carbon in the product. The best thing is just to have a go—mistakes will soon become
obvious and you can always try again.
1
• Use the substituents to help you—some will have changed, but most will be the same or
similar, for example C1 is still easy to spot as the carbon carrying the dimethyl group.
• Use connectivity to help you—again, a C–C bond or two may have broken or formed,
but most of the C–C bonds in the starting material will be there in the product. C1 2 1
and C2 will probably still be next door to one another—C2 was a bridgehead carbon
in the starting material, and there is a bridgehead C attached to C1 in the product;
assume that’s C2.
• C3 and C4 were unsubstituted carbons in the starting material, and are identifiable 7
in the product too. The other easily spotted atom is C7—an unsubstituted C 2 1
3
attached to C2.
4
• C5, C6, and C8 are harder. We can assume that C8 is the =CH2 carbon—it was a
methyl group but perhaps has become involved in an elimination. C5 was attached to
C1, C4, C6, and C8: one of the remaining carbons is attached to C1 and C8, so that 7
seems more likely to be C5, which leaves C6 as the bridgehead, attached as before to 2 1
3
C7 and C5.
5
4 6
Now we have the whole picture and we can assess what has happened in the reaction—
8
which old bonds have broken and which new bonds have formed.

7
1 2 1
7
2 H+ 3
3
HO 5 5
4 6
6 4
8 8
this old bond this new bond is
is broken formed

Numbering the atoms this way identifies the likely point of rearrangement—the only bond
broken is between C4 and C5. Instead we have a new one between C4 and C6: C4 appears to
have migrated from C5 to C6.
Now for the mechanism. The first step will, of course, be loss of water to generate a secondary
cation at C6. The cation is next to a quaternary centre, and migration of any of three bonds
could generate a more stable tertiary carbocation. But we know that the new bond in the prod-
uct is between C4 and C6, so let’s migrate carbon 4. Manipulating the diagrams a bit turns up
a structure remarkably similar to our product, and all we need to do is lose a proton from C8.

rotate structure about 90°

7 7
1 1 1 1 8 2 1 2 1
2 2 2 5 3 3
7 3 7 3 7 3 = 7 2
H2O 5 5 5 = 5 5
6 4 6 4 6
6 6 6 3
4 4 4
8 8 4 8 H 8
8
migrate C4 from C5 to C6 to create tertiary cation