Regioselectivity of the Reactions of Heteroatom-Stabilized Allyl ...

718
and anti 417 γ-adducts in excellent yields and high
diastereoselectivity (ratio 92:8) (Scheme 73). Similar
behavior is shown by 3,4-dihydro-4-oxo-(2H)-pyridine-1-carboxylate
219 (cf. section II.F).
F. Rationalization of Results
There have been numerous investigations on the
regioselectivity of heteroatom-stabilized allylic
anions. 37,42,75,166,224,442-448 However, there is still no
general concept to describe the regioselectivity of the
reaction of electrophiles with these compounds.
The rule of thumb of Still and Macdonald53 is quite
useful for predicting the orientation of electrophilic
attack. They state that allyl anions substituted by
anion-destabilizing groups (OR, NR2) have an increased
electron density at the γ-carbon and hence
favor γ-alkylation, whereas carbonyl compounds react
at the R-terminus. Anion-stabilizing groups (SR,
BR2) should have a complementary charge distribution
and therefore demonstrate R-alkylation and
γ-attack by carbonyl compounds. However, this rule
of thumb does not apply to allyl anions substituted
by strong electron-withdrawing groups and to free
allyl anions; the lithium cation and the allylic anion
must be associated. This rule is also modified by
various other factors, for instance by steric effects or
ionizing cosolvents.
The “allopolarization principle” 449 of Gompper and
Wagner was applied to kinetically controlled reactions.
They rationalize that the change of the selectivity
of a reaction is a function of a change in polarity
of the ambident anion, whereby the “polarity index”
is determined by the relative charge density at the
potential reactive centers. Consequently, donor substituents
favor attack at the γ-terminus, while R-regioselectivity
is observed for acceptor substituents.
However, this concept cannot be applied to reactions
having π-complexes or ion pairs as intermediates,
since the course of their following reactions can no
longer be deduced from the properties of the starting
materials. 449
Pearsons HSAB276,277 was also used to interpret the
outcome of these reactions, but it does not differentiate
between kinetic and thermodynamic control of a
reaction and further it does not take into consideration
that the “hardness” of the heteroatoms has an
influence on the reaction of neutral compounds and
their anions.
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