Exception to Markovnikovs Rule

Alkenes: Structure and

Reactivity

Addition of HBr to alkenes in the presence of

peroxides (ROOR)
! Does not occur significantly with HF, HCl and HI

Based on McMurrys Organic

Chemistry, 7th edition

Syn and Anti Additions

syn addition adding reagent on the same side
anti addition adding reagent on the opposite
side

Halogenation (anti-addition)
Addition of bromine and chlorine

Halogenation (anti-addition)
George Kimball and Irving Roberts observed
anti-stereochemistry

Halogenation (anti-addition)
George Kimball and Irving Roberts observed
anti-stereochemistry
! Reaction intermediate is not a carbocation but
instead a bromonium ion (R2Br+); similarly,
chloronium ion (R2Cl+)

Halogenation (anti-addition)

Halohydrin Formation
Addition of Br2 and Cl2 in the presence of H2O

Mechanism of Halohadrin Formation

from Alkene

Bromohydrin Formation
Often carried out in aqueous dimethyl sulfoxide
CH3SOCH3 (DMSO) and N-bromosuccinimide
(NBS)

Halohydrin Formation
If alkene is unsymmetrical, halogen ends up on
the carbon with greater number of hydrogen
atoms

Acid-catalyzed hydration (Markovnikov

addition of H2O, H+)

Oxymercuration-Demercuration
Alkenes react with mercuric acetate in a mixture
of tetrahydrofuran (THF) and water to produce
(hydroalkyl)mercury compounds

Regioselectivity of OxymercurationDemercuration
Markovnikov addition

Oxymercuration-Demercuration
(Hydroalkyl)mercury compounds can be
reduced to alcohols with sodium borohydride
(NaBH4)

Oxymercuration-Demercuration
Rearrangement seldom occur

Mechanism of Oxymercuration

Mechanism of Oxymercuration

Mechanism of Oxymercuration

Hydroboration-Oxidation (AntiMarkovnikov Syn Hydration)

Anti-Markovnikov hydration of double bond can
achieved through the use of diborane (B2H6) or
solution of borane in tetrahydrofuran
(BH3:THF)

Hydroboration-Oxidation (AntiMarkovnikov Syn Hydration)

Addition of B-H bond of borane to an alkene
then followed by oxidation with basic hydrogen
peroxide

Hydroboration-Oxidation
Alkene reacts with BH3 in THF by rapid addition
to the double bond forming a trialkylborane
When treated with hydrogen peroxides C-B
bonds are broken; OH bonds are formed

BH3-THF complex
Borane is very reactive (boron has only six
electrons). It accepts electrons from THF

Hydroboration-Oxidation (AntiMarkovnikov Syn Hydration)

Boron and hydrogen both add on the same side
(face) of the double bond
! During oxidation, boron is replaced by -OH

Mechanism of Hydroboration-Oxidation

Example
What products would you obtain from reaction
of 2,4-dimethyl-pent-2-ene with:
! BH3 followed by H2O2, OH! Hg(OAc)2, followed by NaBH4

Solution

Hydrogenation: Reduction of Alkenes

Reduction gain of electron density by carbon
! Bond formation of carbon and a less
electronegative atom (C-H)
! Breaking bond between a more electronegative
atom (C-O, C-N, C-X)

Catalytic Hydrogenation

Mechanism of Alkene Hydrogenation

Heterogeneous process reaction takes place on

the surface of insoluble catalyst particle
! Platinum (PtO2) and palladium (Pd/C) are used as
a catalyst

Syn addition

Mechanism of Alkene Hydrogenation

Alkene Hydrogenation

Alkene Hydrogenation

Catalytic hydrogenation of
polyunsaturated fats