Chapter
8
Reac,ons


Prepara,on
of
Alkenes
(8.1)

•  Dehalogena,on

•  Reactants:


–  1.


–  2.


•  Products:


–  1.


 Prepara,on
of
Alkenes
(8.1)

•  Dehalogena,on

•  Reactants:


–  1.
alkyl
halide

–  2.
strong
base

•  Products:


–  1.
alkene
with
loss
of
HX

 Prepara,on
of
Alkenes
(8.1)

•  Dehydra,on

•  Reactants:

–  1.



–  2.

•  Solvent:


–  1.

–  2.

•  Products:


–  1.


 Prepara,on
of
Alkenes
(8.1)

•  Dehydra,on

•  Reactants:

–  1.
alcohol

–  2.
H2SO4

•  Solvent:


–  1.
THF
(Tetrahydrofuran)

–  2.
Heat

•  Products:


–  1.
Alkene
with
loss
of
H2O

 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

Halogena,on
by
radicals


•  Reactants:

–  1.



–  2.


–  3.


•  Intermediate(s):


–  1.

•  Products:


–  1.


 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

Halogena,on
by
radicals


•  Reactants:

–  1.

Br2

–  2.
hv
light

–  3.
alkane

•  Intermediate(s):


–  1.
Br
radical

•  Products:


–  1.
Bromo‐alkane

 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

Halogena,on


•  Reactants:


–  1.


–  2.


•  Intermediate(s):


–  1.


•  Products:

–  1.


•  Stereochemistry:


–  1.


•  Regiochemistry:


–  1.


 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

Halogena,on


•  Reactants:


–  1.
HBr

–  2.
Alkene

•  Intermediate(s):


–  1.
Cyclic
halonium
ion

•  Products:

–  1.
Alkyl
halide

•  Stereochemistry:


–  1.
An,

•  Regiochemistry:


–  1.
Markovnikov

 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Dihalogena,on

•  Reactants:


–  1.


–  2.


•  Intermediate(s):


–  1.


•  Products:


–  1.


•  Stereochemistry:


–  1.


•  Regiochemistry:


–  1.


 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Dihalogena,on

•  Reactants:


–  1.
Br2
or
Cl2

–  2.
Alkene

•  Intermediate(s):


–  1.
Cyclic
halonium
ion

•  Products:


–  1.
1,2
dihaloalkanes


•  Stereochemistry:


–  1.
An,

•  Regiochemistry:


–  1.
Markovnikov

 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Addi,on
of
Hypohalous
Acids

•  Reactants:


–  1.


–  2.

–  3.

•  Solvent:


–  1.


•  Intermediate(s):

–  1.


•  Products:

–  1.



•  Stereochemistry:

–  1.


•  Regiochemistry:


–  1.


•  Notes:


–  1.


–  2.


 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Addi,on
of
Hypohalous
Acids

•  Reactants:


–  1.
Alkene

–  2.
HO‐X

(X
=
Br
[NBS]
or
Cl)

–  3.

H2O

•  Solvent:


–  1.
(if
NBS)
DMSO

•  Intermediate(s):

–  1.
Cyclic
halonium
ion

•  Products:

–  1.

Halohydrin

•  Stereochemistry:

–  1.

An,

•  Regiochemistry:


–  1.
Markovnikov
for
OH

•  Notes:


–  1.
aroma,c
rings
are
inert
to
halohydrin
reagents

–  2.
OH
will
go
to
the
more
highly
subs,tuted
carbon,
because
that
is
the
carboca,on
that

is
made
when
the
halonium
ion
breaks

 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Hydra,on

–  Reactants:

•  1.


•  2.


•  3.


–  Solvent:

•  1.


–  Intermediate(s):

•  1.


–  Products:

•  1.



–  Regiochemistry:

•  1.



–  Notes:


•  1.


 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Hydra,on

–  Reactants:

•  1.
H2O

•  2.
H2SO4

•  3.
Alkene

–  Solvent:

•  1.
Heat

–  Intermediate(s):

•  1.
Carboca,on


–  Products:

•  1.

Alcohol

–  Regiochemistry:

•  1.

Markovnikov

–  Notes:


•  1.
Reac,on
condi,ons
are
too
severe
for
most
molecules.

 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Oxymercura,on

–  Reactants:


•  1.


•  2.


•  3.


–  Solvent:

•  1.


–  Intermediate
1:


•  1.


–  Intermediate
2:


•  1.


–  Step
2:

•  1.


–  Products:


•  1.


–  Regiochemistry:


•  1.


–  Notes:

•  1.


 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Oxymercura,on

–  Reactants:


•  1.
Hg(OAc)2

•  2.
H2O

•  3.
alkene

–  Solvent:

•  1.
THF

–  Intermediate
1:


•  1.
Mercurinium
ion,
add
H2O

–  Intermediate
2:


•  1.
Organomercury
compound

–  Step
2:

•  1.
Cleaved
by
NaBH4
(sodium
borohydride)


–  Products:


•  1.
Alcohol

–  Regiochemistry:


•  1.
Markovnikov
for
OH

–  Notes:


•  1.
The
hydrogen
that
replaces
the
mercurinium
ion
can
aWach
from
either
side,
depending
on
the

exact
circumstances.
Important
because
Borohydra,on
always
adds
the
hydrogen
cis
to
the

hydroxide.

 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Hydrobora,on

•  Reactants:

–  1.


–  2.


•  Solvent:

–  1.


•  Intermediate:


–  1.

•  Step
2:


–  1.


•  Products:

–  1.


•  Stereochemistry:


–  1.


•  Regiochemistry:


–  1.


•  Notes:


–  1.


–  2.


 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Hydrobora,on

•  Reactants:

–  1.
BH3

–  2.
Alkene

•  Solvent:

–  1.
THF

•  Intermediate:


–  1.
Organoborane
(or
trialkylborane)

•  Step
2:


–  1.
Cleaved
by
H2O2
(peroxide),
OH

•  Products:

–  1.
Alcohol
(or
three)

•  Stereochemistry:


–  1.
syn

•  Regiochemistry:


–  1.
non‐Markovnikov

•  Notes:


–  1.
The
mechanism
of
hydrobora,on
involves
a
four‐center,
cyclic
transi,on
state.


–  2.
Hydrogen
is
cis
to
the
hydroxide

 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Reduc,on
of
Alkenes
via
Catalyst

•  Reactants:

–  1.

–  2.


–  3.
or

–  4.
or

–  5.
or

•  Products:


–  1.


•  Stereochemistry:


–  1.

•  Notes:

–  1.


–  2.



 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Reduc,on
of
Alkenes
via
Catalyst

•  Reactants:

–  1.
Alkene

–  2.
H2

–  3.
Pt
or

–  4.
Pd
or

–  5.
Ni
or

•  Products:


–  1.
Alkane

•  Stereochemistry:


–  1.
Syn


•  Notes:

–  1.
The
reac,on
is
sensi,ve
to
the
steric
environment
around
the
double

bond.

–  2.
Alkenes
are
much
more
reac,ve
than
other
func,onal
groups.


 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Peroxyacid‐Epoxida,on

•  Reactants:


–  1.

–  2.


–  3.


•  Products:


–  1.


•  Stereochemistry:


–  1.


•  Notes:


–  1.


–  2.


 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Peroxyacid‐Epoxida,on

•  Reactants:


–  1.
Peroxyacid
(RCO3H)

–  2.
Alkene

–  3.
Strong
acid

•  Products:


–  1.
Epoxide

•  Stereochemistry:


–  1.
Syn

•  Notes:


–  1.
Single
step,
no
intermediate

–  2.
Donated
oxygen
is
the
one
farthest
from
the
carbonyl
group
on
the

peroxyacid
performing
the
dona,on

 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Halohydrin‐Epoxida,on

•  Reactants:


–  1.


–  2.


–  3.


•  Products:


–  1.


•  Stereochemistry:

–  1.

•  Regiochemistry:


–  1.


•  Notes:

–  1.


 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Halohydrin‐Epoxida,on

•  Reactants:


–  1.
Alkene

–  2.
Halohydrin

–  3.
Strong
base

•  Products:


–  1.
Epoxide

•  Stereochemistry:

–  1.
An,

•  Regiochemistry:


–  1.
Markovnikov
for
OH

•  Notes:

–  1.
Same
pathway
as
halonium
ion,
except
base
takes
away
the
halide

 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Acid‐Hydroxyla,on

•  Reactants:


–  1.


–  2.


–  3.


•  Products:

–  1.



–  2.


•  Stereochemistry:


–  1.

 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Acid‐Hydroxyla,on

•  Reactants:


–  1.
Epoxide
ring

–  2.
Hydronium

–  3.
Alkene

•  Products:

–  1.

trans
1,2
dialcohol,
or
diol,
or
glycol
(all
same
thing)

–  2.
Regenerated
acid

•  Stereochemistry:


–  1.
an,
(acid
goes
to
boWom
of
epoxide
ring)

 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Osmium‐Hydroxyla,on

•  Reactants:


–  1.


–  2.


•  Solvent

–  1.

•  Intermediate:


–  1.


•  Step
2:
Cleaved
by

–  1.

or


–  2.

•  Products:


–  1.


•  Stereochemistry:


–  1.


 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Osmium‐Hydroxyla,on

•  Reactants:


–  1.
OsO4

–  2.
Alkene

•  Solvent

–  1.
Pyridine

•  Intermediate:


–  1.
Cyclic
osmate

•  Step
2:
Cleaved
by

–  1.
NMO
or


–  2.
H2O
and
NaHSO3
(sodium
bisulfite)

•  Products:


–  1.
cis
glycol

•  Stereochemistry:


–  1.
Syn

 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Cleavage
of
Carbonyl
Compounds

•  1.


•  2.

•  3.


•  4.


•  5.


•  6.


 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Cleavage
of
Carbonyl
Compounds

•  1.
If
a
double
bonds
is
on
an
open
chain,
then
two
open
chains

result

•  2.
If
a
double
bond
is
on
an
open
chain
that
connects
two
rings,

but
the
double
bond
isn’t
part
of
the
rings,
two
rings
result

•  3.
If
a
ring
(without
a
double
bond)
is
connected
to
an
open
chain

that
contains
double
bond,
one
ring
and
one
open
chain
result

•  4.
If
one
double
bond
is
part
of
a
ring,
one
product
dicarbonyl

open
chain
results

•  5.
If
two
double
bonds
are
part
of
a
ring,
two
dicarbonyl
open

chains
result

•  6.
If
a
ring
with
a
double
bond
is
connected
to
an
open
chain
that

contains
a
double
bond,
two
open
chains
result

 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Ozonolysis
Cleavage:
Reduc,on


•  Reactants:


–  1.


–  2.

•  Intermediate
1:


–  1.


•  Intermediate
2:


–  1.


•  Step
2:


–  1.


»  A.

»  B.


•  Products:


–  1.


»  A.
or

»  B.


•  Notes:

–  1.


–  2.


–  3.


 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Ozonolysis
Cleavage:
Reduc,on

•  Reactants:


–  1.
Alkene

–  2.
O3
(ozone)

•  Intermediate
1:


–  1.
molozonide,
rearranges
to

•  Intermediate
2:


–  1.
ozonide

•  Step
2:


–  1.
ozonide
cleaved
by

»  A.
Zn
metal
in
ace,c
acid
or
in
water

»  B.
(CH3)2S

•  Products:


–  1.


»  A.
Ketone
or

»  B.
Aldehyde

•  Notes:
fragment
rules
apply

–  1.
Tetra
subs,tuted
double
bond
=
2
ketones

–  2.
Tri
subs,tuted
double
bond
=
1
ketone,
1
aldehyde

–  3.
Di
subs,tuted
double
bond
=
2
aldehydes


 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Ozonolysis
Cleavage:
Oxida,on

•  Reactants:


–  1.


–  2.


•  Intermediate
1:


–  1.


•  Intermediate
2:


–  1.


•  Step
2:


–  1.


•  Products:


–  1.


»  A.
or

»  B.


•  Notes:
fragment
rules
apply

–  1.


–  2.


–  3.


 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Ozonolysis
Cleavage:
Oxida,on

•  Reactants:


–  1.
Alkene

–  2.
O3
(ozone)

•  Intermediate
1:


–  1.
molozonide,
rearranges
to

•  Intermediate
2:


–  1.
ozonide

•  Step
2:


–  1.
ozonide
cleaved
by
H2O2
and
OH

•  Products:


–  1.


»  A.
Ketone
or

»  B.
Carboxylic
acid

•  Notes:
fragment
rules
apply

–  1.
Tetra
subs,tuted
double
bond
=
2
ketones

–  2.
Tri
subs,tuted
double
bond
=
1
ketone,
1
Carboxylic
acid

–  3.
Di
subs,tuted
double
bond
=
2
Carboxylic
acids

 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Potassium
Permanganate
Cleavage

•  Reactants:

–  1.


–  2.


•  Solvent:

–  1.


•  Products:

–  1.


•  Notes:
fragment
rules
apply

–  1.


–  2.

–  3.


–  4.


–  5.


 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Potassium
Permanganate
Cleavage

•  Reactants:

–  1.
Alkene

–  2.
KMnO4

•  Solvent:

–  1.
Neutral
or
acidic
solu,on

•  Products:

–  1.
Carbonyl
fragments

•  Notes:
fragment
rules
apply

–  1.
Tetrasubs,tuted
=
two
ketones

–  2.
trisubs,tuted
=
ketone
and
carboxylic
acid

–  3.
disubs,tuted
=
two
carboxylic
acids

–  4.
monosubs,tued
=
carboxylic
acid
and
CO2

–  5.
no
subs,tu,on
=
two
CO2’s

 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Periodic
Acid
Cleavage

•  Reactants:

–  1.


–  2.


–  3.


•  Intermediate(s):


–  1.


•  Products:

–  1.


•  Notes:


–  1.


 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Periodic
Acid
Cleavage

•  Reactants:

–  1.
HIO4

–  2.
H20

–  3.
Glycol

•  Intermediate(s):


–  1.
Cyclic
periodate

•  Products:

–  1.
Carbonyl
fragments

•  Notes:


–  1.
fragment
rules
apply

 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Carbenes
from
Halides

•  Reactants:


–  1.


–  2.


•  Intermediate
1:


–  1.


•  Intermediate
2:


–  1.

•  Step
2:


–  1.


•  Products:


–  1.


•  Stereochemistry:


–  1.


 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Carbenes
from
Halides

•  Reactants:


–  1.
Tri‐halide
(ex:
chloroform)


–  2.
Strong
base

•  Intermediate
1:


–  1.
tri‐halide
anion,
spontaneous
loss
of
a
halide
gives…

•  Intermediate
2:


–  1.
carbene
(neutral,
empty
valence)

•  Step
2:


–  1.
Carbene
and
alkene
react

•  Products:


–  1.
dichlorocyclopropane

•  Stereochemistry:


–  1.
stereospecific;
cis
reactant
=
cis
product,
vice
versa

 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Non‐halogenated
Carbenes
(Simmons‐Smith)

•  Reactants:


–  1.


–  2.


•  Intermediate
:


–  1.


•  Step
2:


–  1.


•  Products:

–  1.



 Addi,on
Reac,on
of
Alkenes
(8.2
–

8.6)

•  Non‐halogenated
Carbenes
(Simmons‐Smith)

•  Reactants:


–  1.
dihalide
(ex:
diiodomethane)

–  2.
Zn(Cu)

•  Intermediate
:


–  1.
Carbenoid
(metal‐complexed
reagent)

•  Step
2:


–  1.
carbenoid
and
alkene
react

•  Products:

–  1.

nonhalogenated
cyclopropane