_oo Gregory R.

ook page + hem ( Exam Reactons

North Dakota State Unversty
REATlONS
lor lna Exam
Reactions for Final Exam
Although you dont need to know all of the mechanisms for these reactions, knowing them
makes it easier to understand the reactions and to figure out a reaction if you forget it. Consult the
lecture notes for more details on the mechanisms and issues of stereo- and regioselectivity.
ELECTROPHILIC ADDITION REACTIONS
HX
X
+
X
OCH
3
HgO
2
CCF
3
NaBH
4
OCH
3
Hg(O
2
CCF
3
)
2
CH
3
OH
R
R
OH
R
O
HgSO
4
H
3
O
+
enol ketone
CH
3
CH
3
O
MCPBA
CH
3
CH
3
OH
Br
Br
2
H
2
O
CH
3
BH
3
H
2
O
2
, OH
-
CH
3
H
OH
CH
3
Hg(OAc)
2 CH
3
OH
H
2
O
NaBH
4
1)
2)
CH
3
OsO
4
CH
3
OH NaHSO
3
OH
1)
2)
_oo Gregory R. ook page hem ( Exam Reactons
North Dakota State Unversty
ELECTROPHILIC SUBSTITUTION REACTIONS
Br
2
FeBr
3
Br
Cl
2
FeCl
3
Cl
I
2
CuI
2
I
HNO
3
H
2
SO
4
NO
2
SO
3
H
2
SO
4
SO
3
H
R-Cl
AlCl
3
R
R Cl
O
AlCl
3
R
O
O
Br
2
CH
3
CO
2
H
O
Br
Br
2
PBr
3
O
OH
O
OH
1)
2) H
2
O
Br
_oo Gregory R. ook page hem ( Exam Reactons
North Dakota State Unversty
NUCLEOPHILIC ADDITION REACTIONS
Ph H
O
Ph H
HO CN HCN
cyanohydrin
KOH
O
HO OH
H
2
O
hydrate
+
H
+
or
-
OH
catalyst
O
R-NH
2
H
+
N
R
H
2
O
+ +
imine
O
R
2
NH
H
+
N
R R
H
2
O
+ +
enamine
O
ROH
H
+
RO OR
+
2
an acetal
1,4-addition
O
CH
3
NH
2
O
NHCH
3
1,4-addition
O O
Ph
1) Ph
2
CuLi
2) H
3
O
+
1,2-addition
O
1) PhMgBr
2) H
3
O
+
HO
Ph
1,2-addition
O
1) PhLi
2) H
3
O
+
HO
Ph
R Cl
O
R Ph
1) PhMgBr
2) H
3
O
+
HO
Ph
_oo Gregory R. ook page ( hem ( Exam Reactons
North Dakota State Unversty
R OCH
3
O
R Ph
1) PhMgBr
2) H
3
O
+
HO
Ph
C N
CH
3
1) CH
3
MgBr
2) H
2
O
O
O
+
Ph
3
P CH
2
phosphonium
ylide
CH
2
+
Ph
3
P O
1,2-addition
O
1) NaBH
4
2) H
3
O
+
HO
H
1,2-addition
O
1) LiAlH
4
2) H
3
O
+
HO
H
The addition of hydrides to carbonyls is also considered reductions and more examples are listed
under reduction reactions.
O
O
MgBr
OH
O
H
3
O
+
MgBr
O C O
SUBSTITUTION REACTIONS (S
N
1)
CH
3
OH
HCl
CH
3
O
H
H
-H
2
O
Cl
CH
3
CH
3
O
HCl
CH
3
O H
Cl
OH
CH
3
Cl
(regioselective like S
N
1 but stereoselective like S
N
2) (also opens with water to make trans diol)
_oo Gregory R. ook page hem ( Exam Reactons
North Dakota State Unversty
SUBSTITUTION REACTIONS (S
N
2)
S
O
Cl Cl OH
H S
O
O Cl Cl
P
Br
Br Br OH
H P
Br
O Br Br
S
O
Cl
OH O
Tos
Tos-Cl
pyridine
Br OH
Si Cl
CH
3
H
3
C
CH
3
Br O
Si
CH
3
CH
3 H
3
C
pyridine
trimethylsilyl
chloride (TMS-Cl)
OH
1) NaH
2) CH
3
I
O CH
3
O
HI
O
H
I
O
H
I
+
O
HCl
O
H
Cl
Cl
OH
O
1) PhMgBr
2) H
2
O
Ph
OH
Ph SH
CH
3
I
Ph S
CH
3
R OH
O
NaOH
R O
O
Na
CH
3
I
R OCH
3
O
O
1) LDA
2) CH
3
I
O
CH
3
_oo Gregory R. ook page hem ( Exam Reactons
North Dakota State Unversty
OEt
O
EtO
O NaOEt, EtOH
R Br
OEt
O
EtO
O
R
OEt
O
H
3
C
O
NaOEt
EtOH
R Br
OEt
O
H
3
C
O
R
SUBSTITUTION REACTIONS (Nucleophilic Aromatic and Nucleophilic Acyl)
Cl
NaOH
25 C
O
2
N NO
2
NO
2
OH
O
2
N NO
2
NO
2
NaOH
340 C
2500 psi
Cl OH
H H
benzyne
intermediate
R OH
O
+ SOCl
2
R Cl
O
+ SO
2
+ HCl
R OH
O
+
R
O
+ HOH
R HO
O Heat
R O
O
R OH
O
HA
R'OH
R OR'
O
R Cl
O
+
R
O
+
NaCl
R NaO
O
R O
O
R Cl
O
+ H
2
O
R OH
O
+ HCl
R Cl
O
+ R'OH
R OR'
O
+ Pyridine-HCl
pyridine
R Cl
O
+ NH
3
R NH
2
O
+ NH
4
Cl 2
R Cl
O
R Ph
O
1)

Ph
2
CuLi
2) H
3
O
+
_oo Gregory R. ook page ; hem ( Exam Reactons
North Dakota State Unversty
+ H
2
O
O
O O
OH
O
2
+
ROH
O
O O
OR
O
+
OH
O
+
NH
3
O
O O
NH
2
O
+
OH
O
+
R OCH
3
O
+ H
2
O
R ONa
O
NaOH (cat)
CH
3
OH
Ph H
HO C N
H
3
O
+
Ph H
HO C
O
OH
R NH
2
O
+ H
2
O
R OH
O
HA (cat)
+ NH
4
A
CH
3
O
I
2
, NaOH
O
O
+ CHI
3
iodoform
ELIMINATION REACTIONS
OH
H
3
C
CH
3
H
2
SO
4
E1
OH
POBr
3
pyridine
E2
NH
2
O
Cl
S
Cl
O
C N
O
Br pyridine
O
_oo Gregory R. ook page 8 hem ( Exam Reactons
North Dakota State Unversty
OXIDATION REACTIONS
R R
OH CrO
3
H
3
O
+
R R
O
R
OH CrO
3
H
3
O
+
R OH
O
PCC
R
OH
R H
O
R
O CrO
3
H
3
O
+
R OH
O
H
R
O
R OH
O
H
Ag
2
O
NH
4
OH
O
KMnO
4
O
OH
O
OH
OH
O
KMnO
4
2
O
H
O
1) O
3
2) Zn, AcOH
+
Ph SH Ph S Ph S
I
2
Ph
S
CH
3
H
2
O
2
Ph
S
CH
3
O
Ph
S
CH
3
O O
H
3
C O
O
H
O
a sulfoxide a sulfone
KMnO
4
CH
3
C
O
OH
_oo Gregory R. ook page , hem ( Exam Reactons
North Dakota State Unversty
KMnO
4
C
O
OH
KMnO
4
C
O
OH
O
REDUCTION REACTIONS
R OH
R H
O
1) NaBH
4
2) H
3
O
+
R OH
R H
O
1) LiAlH
4
2) H
3
O
+
R OH
R OCH
3
O
1) LiAlH
4
2) H
3
O
+
R H
R OCH
3
O
1) DIBAH
2) H
3
O
+ O
R H
R
C
1) DIBAH
2) H
3
O
+ O
N
1) LiAlH
4
2) H
3
O
+
Ph H
HO C N
Ph H
HO
NH
2
R OH
R OH
O
1) LiAlH
4
2) H
3
O
+
R OH
R OH
O
1) BH
3
2) H
3
O
+
_oo Gregory R. ook page +o hem ( Exam Reactons
North Dakota State Unversty
R Cl
O
R OH
1) LiAlH
4
2) H
3
O
+
R Cl
O
R H
O
1) LiAlH(Ot-Bu)
3
2) H
3
O
+
R NH
2
R NH
2
O
1) LiAlH
4
2) H
2
O
O
H
2
N NH
2
KOH
N
NH
2
a hydrazone
H H
Ph SH Ph S Ph S
Zn, H
3
O
+
Pt, 2000 psi
CH
3
or
Rh/C, 15 psi
CH
3
H
2
Pd/C
O
H
2
Pd/C
H
2
NO
2
Pd/C
NH
2
SnCl
2
NO
2
NH
2
H
3
O
+
_oo Gregory R. ook page ++ hem ( Exam Reactons
North Dakota State Unversty
OTHER REACTIONS
NBS
peroxides
Br
also benzylic
bromination
EWG
+
EWG
KNH
2
Cl
+
benzyne
intermediate
O O
H
OH
heat
H
3
O
+
, Heat
HO
O
OEt
O
EtO
O
R
R
+ CO
2
H
3
O
+
, Heat
OEt
O
H
3
C
O
R
H
3
C
O
R
+ CO
2