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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
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
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
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
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
Catalytic Hydrogenation
Syn addition
Alkene Hydrogenation
Alkene Hydrogenation
Catalytic hydrogenation of
polyunsaturated fats