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MECHANISMS

Electrophilic Addition1
In this mechanism, a positive species approaches the double or triple bond and in the first
step forms a bond by donation of the p pair of electrons2 to the electrophilic species to form a
s pair:

The IUPAC designation for this mechanism is

As in electrophilic substitution (p. 658), Y need not actually be a positive ion but can be the
positive end of a dipole or an induced dipole, with the negative part breaking off either during
the first step or shortly after. The second step is a combination of 1 with a species carrying an
electron pair and often bearing a negative charge. This step is the same as the second step of
the SN1 mechanism. Not all electrophilic additions follow the simple mechanism given
above. In many brominations it is fairly certain that 1, if formed at all, very rapidly cyclizes
to a bromonium ion (2):

This intermediate is similar to those encountered in the neighboring-group mechanism of


nucleophilic substitution (see p. 446). The attack of w on an intermediate like 2 is an SN2
step. Whether the intermediate is 1 or 2, the mechanism is called AdE2 (electrophilic

addition, bimolecular). In investigating the mechanism of addition to a double bond, perhaps


the most useful type of information is the stereochemistry of the reaction.3 The two carbons
of the double bond and the four atoms immediately attached to them are all in a plane (p. 9);
there are thus three possibilities. Both Y and W may enter from the same side of the plane, in
which case the addition is stereospecific and syn; they may enter from opposite sides for
stereospecific anti addition; or the reaction may be nonstereospecific. In order to determine
which of these possibilities is occurring in a given reaction, the following type of experiment
is often done: YWis added to the cis and trans isomers of an alkene of the form ABC=CBA.
We may use the cis alkene as an example. If the addition is syn, the product will be the
erythro dl pair, because each carbon has a 50% chance of being attacked by Y:

On the other hand, if the addition is anti, the threo dl pair will be formed:

Of course, the trans isomer will give the opposite results: the threo pair if the addition is syn
and the erythro pair if it is anti. The threo and erythro isomers have different physical

properties. In the special case, where Y W (as in the addition of Br2), the erythro pair is a
meso compound. In addition to triple-bond compounds of the type AC=CA, syn addition
results in a cis alkene and anti addition in a trans alkene. By the definition given on p. 194
addition to triple bonds cannot be stereospecific, although it can be, and often is,
stereoselective. It is easily seen that in reactions involving cyclic intermediates like 2,
addition must be anti, since the second step is an SN2 step and must occur from the back side.
It is not so easy to predict the stereochemistry for reactions involving 1. If 1 has a relatively
long life, the addition should be nonstereospecific, since there will be free rotation about the
single bond. On the other hand, there may be some factor that maintains the configuration, in
which case W may come in from the same side or the opposite side, depending on the
circumstances. For example,the positive charge might be stabilized by an attraction for Y that
does not involve a full bond (see 3).

The second group would then come in anti. A circumstance that would favor syn
addition would be the formation of an ion pair after the addition of Y:4

Since Wis already on the same side of the plane as Y, collapse of the ion pair leads to
syn addition.
Another possibility is that anti addition might, at least in some cases, be caused by the
operation of a mechanism in which attack by Wand Yare essentially simultaneous but from
opposite sides:

This mechanism, called the AdE3 mechanism (termolecular addition, IUPAC


ANAE),5 has the disadvantage that three molecules must come together in the transition
state. However, it is the reverse of the E2 mechanism for elimination, for which the transition
state is known to possess this geometry (p. 1478).
There is much evidence that when the attack is on Br (or a carrier of it), the
bromonium ion 2 is often an intermediate and the addition is anti. As long ago as 1911,
McKenzie and Fischer independently showed that treatment of maleic acid with bromine
gave the dl pair of 2,3-dibromosuccinic acid, while fumaric acid (the trans isomer) gave the
meso compound.6 Many similar experiments have been performed since with similar results.
For triple bonds, stereoselective anti addition was shown even earlier. Bromination of
dicarboxyacetylene gave 70% of the trans isomer.7

There is other evidence for mechanisms involving 2. We have already mentioned (p.
449) that bromonium ions have been isolated in stable solutions in nucleophilic substitution
reactions involving bromine as a neighboring group. Such ions have also been isolated in
reactions involving addition of a Br species to a double bond.8 The following is further
evidence. If the two bromines approach the double bond from opposite sides, it is very
unlikely that they could come from the same bromine molecule. This means that if the
reaction is performed in the presence of nucleophiles, some of these will compete in the
second step with the bromide liberated from the bromine. It has been found, indeed, that
treatment of ethylene with bromine in the presence of chloride ions gives some 1-chloro-2bromoethane along with the dibromoethane.9 Similar results are found when the reaction is
carried out in the presence of water (15-40) or of other nucleophiles.10 Ab initio molecular
orbital studies show that 2 is more stable than its open isomer 1 (Y = Br).11 There is evidence
that formation of 2 is reversible.12
However, a number of examples have been found where addition of bromine is not
stereospecifically anti. For example, the addition of Br2 to cis- and trans-1- phenylpropenes
in CCl4 was nonstereospecific.13 Furthermore, the stereospecificity of bromine addition to
stilbene depends on the dielectric constant of the solvent. In solvents of low dielectric
constant, the addition was 90100% anti, but with an increase in dielectric constant, the

reaction became less stereospecific, until, at a dielectric constant of _35, the addition was
completely nonstereospecific.14
Likewise in the case of triple bonds, stereoselective anti addition was found in bromi
nation of 3-hexyne, but both cis and trans products were obtained in bromination of
phenylacetylene.15 These results indicate that a bromonium ion is not formed where the open
cation can be stabilized in other ways (e.g., addition of Br to 1-phenylpropene gives the ion
PhC_HCHBrCH3, which is a relatively stable benzylic cation) and that there is probably a
spectrum of mechanisms between complete bromonium ion (2, no rotation) formation and
completely open-cation (1, free rotation) formation, with partially bridged bromonium ions
(3, restricted rotation) in between.16 We have previously seen cases (e.g., p. 461) where
cations require more stabilization from outside sources as they become intrinsically less
stable themselves.17 Further evidence for the open cationmechanism where aryl stabilization
is present was reported in an isotope effect study of addition of Br2 to ArCH=CHCHAr (Ar
= p-nitrophenyl, Ar= p-tolyl). The 14C isotope effect for one of the double-bond carbons
(the one closer to the NO2 group) was considerably larger than for the other one.18
When the -bond of an alkene attacks Cl,19 I,20 and RS,21 the result is similar to
that when the electrophile is Br; there is a spectrum of mechanisms between cyclic
intermediates and open cations. As might be expected from our discussion in Chapter 10 (p.
446), iodonium ions compete with open carbocations more effectively than bromonium ions,
while chloronium ions compete less effectively. There is kinetic and spectral evidence that at
least in some cases, for example, in the addition of Br2 or ICl, the electrophile forms a
complex with the alkene before a covalent bond is formed.22
When the electrophile is a proton,23 a cyclic intermediate is not possible, and the
mechanism is the simple AH AN process shown before

This is an A-SE2 mechanism (p. 525). There is a great deal of evidence24 for it,
including:
1. The reaction is general-acid, not specific-acid-catalyzed, implying ratedetermining proton
transfer from the acid to the double bond.25

2. The existence of open carbocation intermediates is supported by the contrast in the pattern
of alkyl substituent effects26 with that found in brominations, where cyclic intermediates are
involved. In the latter case, substitution of alkyl groups on H2C=CH2 causes a cumulative
rate acceleration

until all four hydrogens have been replaced by alkyl groups, because each group helps to
stabilize the positive charge.27 In addition of HX, the effect is not cumulative. Replacement
of the two hydrogens on one carbon causes great rate increases (primary ! secondary ! tertiary
carbocation), but additional substitution on the other carbon produces little or no
acceleration.28 This is evidence for open cations when a proton is the electrophile.29
3. Open carbocations are prone to rearrange (Chapter 18). Many rearrangements have been
found to accompany additions of HX and H2O.30
It may also be recalled that vinylic ethers react with proton donors in a similar manner
(see 10-6).
The stereochemistry of HX addition is varied. Examples are known of predominant
syn, anti, and nonstereoselective addition. It was found that treatment of 1,2
dimethylcyclohexene (4) with HBr gave predominant anti addition, 31 while addition of
water to 4 gave equal amounts of the cis and trans alcohols:32

On the other hand, addition of DBr to acenaphthylene (5) and to indene and 1-phenylpropene
gave predominant syn addition.33

In fact, it has been shown that the stereoselectivity of HCl addition can be controlled by
changing the reaction conditions. Addition of HCl to 4 in CH2Cl2 at -98C gave
predominantly syn addition, while in ethyl ether at 0_C, the addition was mostly anti.34
Addition of HX to triple bonds has the same mechanism, although the intermediate
in this case is a vinylic cation, 6.35

In all these cases (except for the AdE3 mechanism), we assumed that formation of the
intermediate (1, 2, or 3) is the slow step and attack by the nucleophile on the intermediate is
rapid, and this is probably true in most cases. However, some additions have been found in
which the second step is rate determining.36

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