Synthesis Road Map Problems

ANSWER:

The tricky step here is the combined hydrogenation/isomerisation. The change in molecular
formula tells you that only one of the two alkenes is reduced (presumably, if the reaction had
been left longer, the other one would also hydrogenate). We expect the more stericallyaccessible alkene to react fastest, but also note that the doubly conjugated alkene is probably
further deactivated. Notice also that hydrogenation should occur from the face opposite to the
angular methyl group on the ring junction.
The NMR signals that are reported are not consistent with the product that
is initially formed by the hydrogenation, however. This product has no
vinylic hydrogens, but it does contain a CH-CH2-CH2 sequence in which
all the methylene protons are diastereotopic and hence distinct. This does

not fit with the reported signals, where the signal at 6.8 must be vinylic. Further, the singlet at
2.8 suggests a proton adjacent to a double bond but with no nearest neighbours. The ddd signals
at 2.0 and 1.8 also suggest protons next to a double bond but having one additional neighbour.
These signposts guide us to the correct product, in which the double bond is conjugated to only
one ester group. This occurs simply by protonation/deprotonation.
It might seem surprising that the thermodynamic product seems to be less conjugated, but
appearances can be deceiving. If you look at a 3-D model of the initial hydrogenation product,
you will notice that it is unlikely that both ester groups can be conjugated with the alkene
because of steric conflicts. Thus, isomerising the double bond doesnt really penalize the
compound, but it does relieve strain. A rough modeling calculation suggests that the difference
in energy is roughly 0.5-1.0 kcal mol-1.

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