Rearrangement of Carbocations:

The formation of carbocations is sometimes accompanied by a structural rearrangement.

Such rearrangements take place by a shift of a neighboring alkyl group or hydrogen, and
are favored when the rearranged carbocation is more stable than the initial cation. The
addition of HCl to 3,3-dimethyl-1-butene, for example, leads to an unexpected product, 2-
chloro-2,3-dimethylbutane, in somewhat greater yield than 3-chloro-2,2-dimethylbutane,
the expected Markovnikov product. This surprising result may be explained by a
carbocation rearrangement of the initially formed 2º-carbocation to a 3º-carbocation by a
1,2-shift of a methyl group. Such rearrangements take place by a shift of a neighboring
alkyl group or hydrogen, and are favored when the rearranged carbocation is more stable
than the initial cation.

minor major
Another factor that may induce rearrangement of carbocation intermediates is ring strain. The addition of
HCl to α-pinene, the major hydrocarbon component of turpentine, gives the rearranged product, bornyl
chloride, in high yield. As shown in the following equation, this rearrangement converts a 3º-carbocation
to a 2º-carbocation, a transformation that is normally unfavorable. However, the rearrangement also
expands a strained four-membered ring to a much less-strained five-membered ring, and this relief of
strain provides a driving force for the rearrangement. The atom numbers (colored red) for the pinene
structure are retained throughout the rearrangement to help orient the viewer. The green numbers in the
final product represent the proper numbering of this bicyclic ring system

3o carbocation 2o carbocation

The propensity for structural rearrangement shown by certain molecular constitutions, as illustrated
above, serves as a useful probe for the intermediacy of carbocations in a reaction.
Addition of Lewis Acids
The proton is not the only electrophilic species that initiates addition reactions to the double bond.
Lewis acids like the halogens, boron hydrides and certain transition metal ions are able to bond to the
alkene π-electrons, and the resulting complexes rearrange or are attacked by nucleophiles to give
addition products. The electrophilic character of the halogens is well known. Although fluorine is
uncontrollably reactive, chlorine, bromine and to a lesser degree iodine react selectively with the
double bond of alkenes. The addition of chlorine and bromine to alkenes, as shown in the following
general equation, proceeds by an initial electrophilic attack on the alkene π-electrons of the double
bond. Iodine adds reversibly to double bonds, but the equilibrium does not normally favor the addition
product, so it is not a useful preparative method. Dihalo-compounds in which the halogens are
juxtaposed in the manner shown are called vicinal, from the Latin vicinalis, meaning neighboring

Other halogen containing reagents which add to double bonds include hypohalous acids, HOX, and
sulfenyl chlorides, RSCl. These reagents are unsymmetrical, so their addition to unsymmetrical double
bonds may in principle take place in two ways. In practice, these addition reactions are regioselective,
with one of the two possible constitutionally isomeric products being favored. The electrophilic
moiety of these reagents is the halogen.
The regioselectivity of the above reactions may be explained by the same mechanism we used to rationalize
the Markovnikov rule. Thus, bonding of an electrophilic species to the double bond of an alkene should
result in preferential formation of the more stable (more highly substituted) carbocation, and this
intermediate should then combine rapidly with a nucleophilic species to produce the addition product. This
is illustrated by the following equation

electrophilic and nucleophilic moieties, as shown on the right.

In the case of hypochlorous and hypobromous acids (HOX),
these weak Brønsted acids (pKa's ca. 8) do not react as proton
donors; and since oxygen is more electronegative than chlorine
or bromine, the electrophile will be a halide cation. The
nucleophilic species that bonds to the intermediate carbocation
is then hydroxide ion, or more likely water (the usual solvent for
these reagents), and the products are called halohydrins.
Sulfenyl chlorides add in the opposite manner because the
electrophile is a sulfur cation, RS(+), whereas the nucleophilic
moiety is chloride anion (chlorine is more electronegative than
sulfur)
Stereoselectivity in Addition Reactions to Double Bonds:
Addition reactions to this function might occur in three different
ways, depending on the relative orientation of the atoms or groups
that add to the carbons of the double bond: (i) they may bond
from the same side, (ii) they may bond from opposite sides, or (iii)
they may bond randomly from both sides. The first two
possibilities are examples of stereoselectivity, the first being
termed syn-addition, and the second anti-addition. Since initial
electrophilic attack on the double bond may occur equally well
from eitherside, it is in the second step (or stage) of the reaction
(bonding of the nucleophile) that stereoselectivity may be imposed

If the two-step mechanism described above is correct, and if the carbocation intermediate is
sufficiently long-lived to freely-rotate about the sigma-bond component of the original double
bond, we would expect to find random or non-stereoselective addition in the products. On the
other hand, if the intermediate is short-lived and factors such as steric hindrance or neighboring
group interactions favor one side in the second step, then stereoselectivity in product formation is
likely. The following table summarizes the results obtained from many studies, the formula HX
refers to all the strong Brønsted acids. The interesting differences in stereoselectivity noted here
provide further insight into the mechanisms of these addition reactions.
Addition Reactions Initiated by Electrophilic Halogen
The halogens chlorine and bromine add rapidly to a wide variety of alkenes without inducing the kinds
of structural rearrangements noted for strong acids (first example below). The stereoselectivity of these
additions is strongly anti, as shown in many of the following examples.
Anti-addition to cis-2-butene gives the racemic product, whereas anti-addition to the trans-isomer
gives the meso-diastereomer. We can account both for the high stereoselectivity and the lack of
rearrangement in these reactions by proposing a stabilizing interaction between the developing
carbocation center and the electron rich halogen atom on the adjacent carbon. This interaction,
which is depicted for bromine in the following equation, delocalizes the positive charge on the
intermediate and blocks halide ion attack from the syn-location

The stabilization provided by this halogen-carbocation bonding makes rearrangement unlikely, and in
a few cases three-membered cyclic halonium cations have been isolated and identified as true
intermediates. A resonance description of such a bromonium ionintermediate is shown below. The
positive charge is delocalized over all the atoms of the ring, but should be concentrated at the more
substituted carbon (carbocation stability), and this is the site to which the nucleophile will bond
Syn- and anti-dihydroxylation of olefins:
OsO4 and KMnO4 mediated dihydroxylation:
Hydroboration oxidation of alkenes:

Reaction type: Electrophilic Addition

Summary.
Overall transformation : C=C to H-C-C-OH
Reagents (two steps) 1. BH3 or B2H6 then 2) NaOH/ H2O2
Regioselectivity : Anti-Markovnikov, since the B is the electrophile.
Stereoselectivity : Syn since the C-B and C-H bonds form simultaneously from the BH3.
The alcohol is formed over a series of steps involving the B center (see below), with retention of
configuration at the C.
Compliments simple hydration with opposite regiochemistry and stereospecificity
Mechanism of hydroboration-oxidation
Oxymercuration-Demercuration of Alkenes

Reaction type: Electrophilic Addition

Summary
Overall transformation : C=C to H-C-C-OH
This is an alternative method for hydrating alkenes to give alcohols
Typical reagents are mercury acetate, Hg(OAc)2 in aqueous THF
Unfortunatley, mercury compounds are generally quite toxic
Regioselectivity predicted by Markovnikov's rule (most highly substituted alcohol)
The reaction is not stereoselective
Reaction proceeds via the formation of a cyclic mercurinium ion (compare
with bromination of alkenes)
The mercurinium is opened by the attack of water to complete the oxy-mercuration.
Demercuration is effected by a reduction using sodium borohydride, NaBH4
Epoxidation of Alkenes

Reaction type: Electrophilic Addition

Summary
Overall transformation : C=C to epoxide
Reagent : a peracid or peroxyacid, RCO3H
Regioselectivity : not relevant since both new bonds are the same, C-O
Stereoselectivity : syn since the two new C-O σ bonds form at the same time from the peracid.
The reaction is an example of a concerted process (i.e. all bonding changes occur in one step)
Relative reactivity (relative rates) : H2C=CH2 (1), CH3CH=CH2 (24), CH3CH=CHCH3 (500),
(CH3)2C=CHCH3 (6500)
The relative rates reflect the increased nucleophilicity of the alkene (due to the electron donating alkyl
groups)
Since the reaction is concerted, the stereochemistry of the alkene is preserved in the product.
For example if the alkyl groups of the alkene are cis- then they are also cis- in the epoxide and trans-
alkenes give trans-epoxides
Peroxycarboxylic acids are generally unstable. An exception is meta-chloroperoxybenzoic
acid, shown in the mechanism above. Often abbreviated MCPBA, it is a stable crystalline
solid. Consequently, MCPBA is popular for laboratory use. However, MCPBA can be
explosive under some conditions
Ozonolysis

Ozonolysis is an efficient way of oxidizing alkenes (and alkynes as well) into their
corresponding aldehydes and ketones
Other reducing agents: Zn/H2O, Ph3P