Chapter 8 Reactions and Mechanisms

Mechanism Reactants & reagents Substituents of Stereochemistry Intermediate? Rearrange Regiospecific? Addition type
product ments? Syn/Anti Relevant
Inorganic
Cis/Trans products?
Halogenation Alkene + Br2/Cl2 Trans vicinal 2nd part of the reaction Bromonium No Anti Anti
(Chlorination + dihalides is SN2 resulting in a Cation (+) Markovnikov
Bromination) pair of enantiomers
in CCl4 racemic m.) (Looks like a
cyclopropane)
(or meso compound)
Halohydrin Alkene + Br2/Cl2 Trans Halide on less 2nd part of the reaction Bromonium No Anti Anti
substituted carbon is SN2 resulting in a Cation (+)
in H2Oor aqueous agent and OH on more pair of enantiomers
( OH + something with substituted carbon (racemic m.) if (Looks like a
hydrogen) reactant is cis cyclopropane)
X + OH
(or meso compound if
substrate is trans)
Carbene Alkene + carbene (:CX2) Cyclopropane ring Pair of enantiomers No No Trans Anti
addition with X & X attached (racemic mixture) f Cyclo-
to same carbon reactant is cis propane

(or meso compound if

substrate is trans)
Simmons-Smith ZnI2 (driving
reaction force
Option A: Two adjacent OH Starting material cis = Yes No Cis – diol Syn addition
SYN OsO4 on Sulfur & groups (vicinal dial) meso compound
Dihydroxylation Hydrogen compound Cyclic Syn
Cis-diol Starting material trans intermediate
Option B: = racemic mixture
KMnO4 [COLD]/+
0- b-
OH- & H2O
Dihydroxylation 1. KMnO4 [HOT] Unsubstituted = CO2 Yes

+ basic conditions + H3O (Important) Monosubstituted =

Carboxylic acid
0- b-
Disubstituted =
Ketone
Mechanism Reactants & reagents Substituents of Stereochemistry Intermediate? Rearrange Cis/Trans Addition Type Inorganic
product ments? product Regiospecific? products?

Acid catalyzed A Hydrogen on the Carbocation YES Acid reforms

hydration of an Alkene + water in less substituted intermediate Carbocatio at the end
alkene presence of carbon and an OH on n may (catalyst)
the more substituted rearrange H3O+
Dilute acid carbon
(H3O+/H2SO4) (H + OH)

Ozonolysis (1) O3 Unsubstituted = formaldehyde

Monsubstituted = aldehyde
Reductive vs. Reductive (Lots of Disubtituted = ketone
Oxidation Hydrogens):
conditions
(2)

Zn/HOAC or DMS or
Zn/H2O or
(CH3)2S
Hydrohalogenati Alkene + H-X Racemic Mixture produced Achiral YES Markovnikov
on Intermediate addition
carbocation
Addition of Alkene + H2SO4 Carbocation Markovnikov
Sulfuric Acid to intermediate addition
Alkenes
Oxymercuration no free NO Markovnikov
/Demercuration carbocation addition
(partial
carbocation)

Hydroboration- no Syn addition ANTI

Oxidation Markovnikov
addition
 Alkene  Alkane
Halogenation (chlorination +
bromination)
Halohydrin formation
Acid catalyzed hydration

Reactions with water that end

up with an alcohol
Halohydrin formation
Acid Catalyzed hydration
Oxymercuration
demercuration

Reaction Reagents
Syn 1,2-Dihydroxylation Either OsO4
or KMnO4 (COLD)
OXIDATIVE CLEAVAGE
Oxidation of alkene KMnO4 (HOT)
Ozonolysis (1) O3 in CH2Cl2 -78 degrees Celcius

Workup with Zinc in acetic acid

(2) Zn/HOAc
 Markovikov Addition Anti-Markovikov Addition
Acid Catalyzed Hydration of an alkene Halogenation