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alcohols
X 2
( B )
X 2 / H 2 O ( B
)
1) BH3 , 2) H2O2 , NaOH (C, D)
1) Hg(OAc)2 , H2O, 2) NaBH4 , (A)
H3O+ /H2O (A)
H X ( A )
H2 /Pd, Pt,or Ni (D)
vicinaldihaloalkanes
halohydrins
1) OsO4 (D) , 2) NaHSO3 vicinaldiols
aldehydes/ ketones
alkenesalkanes
1) O3 , 2) (CH3)2S
haloakanes
ROADMAP FOR REACTIONS Chapter 6
Reactions that cleave carbon-carbon
bonds are indicated by reagents
that are circled.
(A)
(B)
(C)
(D)
(E)
(F)
(G)(H)
( I )
(J)
(K)
(L)
(M)
(N)
(O)
Regiochemistry: Markovnikov addition to a bond
Stereochemistry: anti-addition
Regiochemistry: non-Markovnikov addition to a bond
Stereochemistry: syn-addition
Works well for methyl and 1° haloalkanes
Stereochemistry: gives cis -alkenes as products
Stereochemistry: gives trans -alkenes as productsReactivity of C–H bonds follows 3° > 2° > 1°
Works for methyl, 1°, and 2° haloalkanes
Works for 2° and 3° haloalkanes, may see rearrangements
Works for all haloalkanes except methyl, although a bulky
(non-nucleophilic) base must be used for 1° haloalkanes.
Regiochemistry: follows Zaitzev’s rules so the more substituted
alkene predominates. Stereochemistry: requirement for the
X and H to be eliminated with anti-periplanar geometry.
PBr3 and SOX2 works for methyl, 1°, and 2° haloalkanes.
HX can give rearrangements.
For 1° alcohols
For 2° alcohols
Regiochemistry: the product with the more
substituted alkene predominates
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Chapter 6Key:
Carbon-carbon bond forming
reactions are indicated by reagents
written with solid backgrounds
and white lettering.
Reactions that cleave carbon-carbon
bonds are indicated by reagents that are circled.
Chapter 7
ROADMAP FOR REACTIONS Chapters 6 7
alcohols
N a N H 2
/ N H 3
N a
/ N H 3
( G )
2X2 1) (sia)2BH, 2) H2O
2, NaOH (C)
1) BH3, 2) H2O
2, NaOH
H2SO4, HgSO4 (A)
HX (A)
H 2
/ L i n d l a r C a t .
( F )
H 2
/ P d ,
P t ,
N i
vicinaldihaloalk anes
halohydrins
vicinaldiols
geminal
dihaloalk anes
vicinaltetr
ahaloa
lk anes
aldehydes / k etones
alk enes
alk anes
C R
( E )
N a C
alk ynes
haloak anes
X 2
( B )
X 2
/ H 2 O
( B )
1) BH3, 2) H2O2, NaOH (C, D)
1) Hg(OAc)2, H2O, 2) NaBH4, (A)
H3O+ / H2O (A)
H X
( A )
H2 / Pd, Pt,or Ni (D)
1) OsO4 (D), 2) NaHSO3
1)O3, 2) (CH3)2S
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allylichalides
alcohols
R C
N a N H 2 / N H 3
N a / N H 3
( G )
2X2 1) (sia)2BH, 2) H2O2 , NaOH (C)
1) BH3 , 2) H2O2 , NaOH
H2SO4 , HgSO4 (A)
HX (A)
H 2 / L i n d l a r C a t . ( F )
H 2 / P d , P t , N i
X 2
( B )
X 2 / H 2 O ( B
)
1) BH3 , 2) H2O2 , NaOH (C, D)
1) Hg(OAc)2 , H2O, 2) NaBH4 , (A)
H3O+ /H2O (A)
X2 , hv or heat (H)
H X ( A )
H2 /Pd, Pt,or Ni (D)
H B r , p e r o x i d e s ( C )
NBS (O)
Chapter 6
Key:
Carbon-carbon bond forming
reactions are indicated by reagents
written with solid backgrounds
and white lettering.
Reactions that cleave carbon-carbon
bonds are indicated by reagents that are circled.
Chapter 7
Chapter 8
vicinaldihaloalkanes
halohydrins
1) OsO4 (D) , 2) NaHSO3 vicinaldiols
geminal
dihaloalkanes
vicinal
tetrahaloalkanes
aldehydes/ ketones
alkenesalkanes
C R
( E )
N a C
alkynes
1) O3 , 2) (CH3)2S
haloakanes
ROADMAP FOR REACTIONS Chapters 6 7 8
(A)
(B)
(C)
(D)
(E)
(F)
(G)(H)
( I )
(J)
(K)
(L)
(M)
(N)
(O)
Regiochemistry: Markovnikov addition to a bond
Stereochemistry: anti-addition
Regiochemistry: non-Markovnikov addition to a bond
Stereochemistry: syn-addition
Works well for methyl and 1° haloalkanes
Stereochemistry: gives cis -alkenes as products
Stereochemistry: gives trans -alkenes as productsReactivity of C–H bonds follows 3° > 2° > 1°
Works for methyl, 1°, and 2° haloalkanes
Works for 2° and 3° haloalkanes, may see rearrangements
Works for all haloalkanes except methyl, although a bulky
(non-nucleophilic) base must be used for 1° haloalkanes.
Regiochemistry: follows Zaitzev’s rules so the more substituted
alkene predominates. Stereochemistry: requirement for the
X and H to be eliminated with anti-periplanar geometry.
PBr3 and SOX2 works for methyl, 1°, and 2° haloalkanes.
HX can give rearrangements.
For 1° alcohols
For 2° alcohols
Regiochemistry: the product with the more substituted alkene
predominates
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allylichalides
alcohols
N a C N
( I )
C L i ( E )
R C
N a H R 2 ( I )
N a N 3 ( I )
N a S R ( I )
N a S H (
I )
N a O H ( E
)
H 2 O , a c i d ( J )
N a O R ( E )
H O R , a c i d ( J )
N a N H 2 / N H 3
N a / N H 3 ( G )
2X2 1) (sia)2BH, 2) H2O2 , NaOH (C)
1) BH3 , 2) H2O2 , NaOH
H2SO4 , HgSO4 (A)
HX (A)
H 2 / L i n d l a r C a t . ( F )
H 2 / P d , P t , N i
X 2 ( B )
X 2 / H 2 O ( B
)
1) BH3 , 2) H2O2 , NaOH (C, D)
1) Hg(OAc)2 , H2O, 2) NaBH4 , (A)
H3O+ /H2O (A)
X2 , hv or heat (H)
H X ( A )
H2 /Pd, Pt,or Ni (D)
N a O R ( K )
H B r , p e r o x i d e s ( C )
NBS (O)
Chapter 6
Key:
Carbon-carbon bond forming
reactions are indicated by reagents
written with solid backgrounds
and white lettering.
Reactions that cleave carbon-carbon
bonds are indicated by reagents that are circled.
Chapter 7
Chapter 8
Chapter 9
vicinaldihaloalkanes
halohydrins
1) OsO4 (D) , 2) NaHSO3 vicinaldiols
geminal
dihaloalkanes
vicinal
tetrahaloalkanes
aldehydes/ ketones
alkenes
alkylazides
aminesnitriles thioethersthiols
alkanes
C R
( E )
N a C
alkynes
1) O3 , 2) (CH3)2S
haloakanes
ethers
ROADMAP FOR REACTIONS Chapters 6 7 8 9
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allylichalides
alcohols
N a
C N
( I )
C L i ( E )
R C
N a
H R
2
(
I
)
N a
N 3
(
I
)
N a
S R
(
I
)
N a
S H
(
I
)
N a
O H
( E )
H 2
O ,
a c
i d ( J )
N a
O R ( E )
H O R
, a c
i d ( J )
N a
N H
2 / N H
3
N a
/ N H
3 ( G )
H 2
C r O
4 ( N )
H I O
4
H X
o r
P B r 3 o r
S O C l 2 ( L )
H3PO4
H 2
C r O 4
P C C ( M )
2X2 1) (sia)2BH, 2) H2O2 , NaOH (C)
1) BH3 , 2) H2O2 , NaOH
H2SO4 , HgSO4 (A)
HX (A)
H 2
/ L i n d l a r
C a
t . ( F )
H 2
/ P d
, P t , N i
X 2
( B )
X 2
/ H 2
O (
B )
1) BH3 , 2) H2O2 , NaOH (C, D)
1) Hg(OAc)2 , H2O, 2) NaBH4 , (A)
H3O+ /H2O (A)
X2 , hv or heat (H)
H X ( A )
H2 /Pd, Pt,or Ni (D)
N a
O R ( K )
H B r , p e r o x
i d e s ( C )
NBS (O)
Chapter 6
Key:
Carbon-carbon bond forming
reactions are indicated by reagents
written with solid backgrounds
and white lettering.
Reactions that cleave carbon-carbon
bonds are indicated by reagents
that are circled.
Chapter 7
Chapter 8
Chapter 9
Chapter 10
vicinaldihaloalkanes
halohydrins
1) OsO4 (D) , 2) NaHSO3 vicinaldiols
carboxylicacids
geminal
dihaloalkanes
vicinal
tetrahaloalkanes
aldehydes/ ketones
alkenes
alkylazides
aminesnitriles thioethersthiols
alkanes
C R ( E )
N a
C
alkynes
1) O3 , 2) (CH3)2S
haloakanes
ethers
ROADMAP FOR REACTIONS Chapters 6 7 8 9 10
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Chapter 6
Key:
C a r b o n - c a r b o n b o nd f o r m i ng
r ea c t i o ns a r e i nd i c a t e d b y r ea g e n t s
w r i tt e n w i t h s o li d b a c k g r o unds
a nd w h i t e l e tt e r i ng .
R ea c t i o ns t h a t c l ea v e c a r b o n - c a r b o n
b o nds a r e i
nd i c a t e
d
b y r ea
g e n
t s
t h a t a r e c i r c l e d .
Chapter 7
Chapter 8
Chapter 9
Chapter 10
Chapter 11
ROADMAP FOR REACTIONS Chapters 6 7 8 9 10 11
allylic
halides
alcohols
N a C N
(
I
)
C L i
( E )
R C
N a H R 2
(
I
)
N a N 3
(
I
)
N a S R (
I
)
N a S H (
I
)
N a O H ( E )
H 2 O , a c i d (
J )
N a O R
( E )
H
O R , a c i d (
J )
N a N H 2
/ N H 3
N a
/ N H 3
( G )
H 2 C r O
4
( N )
H I O
4
H X
o r P B r 3 o r S O C l 2
( L )
H3PO4
H 2 C r O 4
P C C
( M )
2X2 1) (sia)2BH, 2) H2O
2, NaOH (C)
1) BH3, 2) H2O
2, NaOH
H2SO4, HgSO4 (A)
HX (A)
H 2
/ L i n d l a r C a t .
( F )
H 2
/ P d ,
P t ,
N i
X 2
( B )
X 2
/ H 2 O ( B )
1) BH3, 2) H2O2, NaOH (C, D)
1)Hg(OAc)2, H2O, 2) NaBH4, (A)
H3O+ / H2O (A)
H3O+ / H2O
X2, hv or heat (H)
H X
( A )
H2 / Pd, Pt,or Ni (D)
N a O R ( K )
H B r , p e r o x
i d e s ( C )
NBS (O)
vicinal
dihaloalk anes
halohydrins
1)OsO4 (D), 2) NaHSO3 vicinal
diols
epoxides
silyl
ethers
carboxylic
acids
vicinal
aminoalcohols
geminal
dihaloalk anes
vicinal
tetraha
loa
lk an
es
aldehydes / k etones
alk enes
alk yl
azidesaminesnitriles thioethersthiols
HI
ROH / acid (J)
1) Cl2, H2O, 2) NaOH, H2O
1 ) L i A l H 4
2 ) H 2 O
t - B u M e 3 S i C l / p y r i d i n e
m-CBPA
alk anes
C R ( E )
N a C
alk ynes
1)O3, 2) (CH3)2S
haloak anes
ethers
N H 3
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ROADMAP FOR REACTIONS
C a r b o n - c a r b o n b o nd f o r m i ng
r ea c t i o ns a r e i nd i c a t e d b y
r ea g e n t s w r i tt e n w i t h s o li d
b a c k g r o unds a nd w h i t e l e tt e r i ng .
Chapter 15
cyclopropanes
geminal dihalocyclopropanes
alk enes
haloalk anes alcohols
CHX3
(CH3)3COK
1)Mg, 2) , 3)H3O+ / H2O
CH2I2
Zn (Cu)
R2CuLi
O
(A)
(B)
(C)
(D)
(E)
(F)
(G)
(H)
( I )
(J)
(K)
(L)
(M)
(N)
(O)
Regiochemistry: Markovnikov addition to a bond
Stereochemistry: anti-addition
Regiochemistry: non-Markovnikov addition to a bond
Stereochemistry: syn-addition
Works well for methyl and 1° haloalkanes
Stereochemistry: gives c i s -alkenes as products
Stereochemistry: gives t r a ns -alkenes as products
Reactivity of C–H bonds follows 3° > 2° > 1°
Works for methyl, 1°, and 2° haloalkanes
Works for 2° and 3° haloalkanes, may see rearrangements
Works for all haloalkanes except methyl, although a bulky
(non-nucleophilic) base must be used for 1° haloalkanes.
Regiochemistry: follows Zaitzev’s rules so the more substituted
alkene predominates. Stereochemistry: requirement for the
X and H to be eliminated with anti-periplanar geometry.
PBr3 and SOX2 works for methyl, 1°, and 2° haloalkanes.
HX can give rearrangements.
For 1° alcohols
For 2° alcohols
Regiochemistry: the product with the more substituted alkene
predominates
vinyl halides
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ROADMAP FOR REACTIONS
Key:
Chapter 15
Carbon-carbon bond forming
reactions are indicated by
reagents written with solid
backgrounds and white lettering.
Chapter 16
Chapters 15 16
H 3 O + / H 2 O
B r 2 , a c i d
H3O+ /H2O
R O H / H +
ROH/H+
cyclopropanes
geminal dihalocyclopropanes
acetals
aldehydes/ ketones
alkenes
haloalkanes alcohols
CHX3
(CH3)3COK
1) Mg, 2) , 3) H3O+ /H2O
CH2I2
Zn (Cu)
1) RC2) H3O+ /H2O
CNa
O
1 ) R M g X , 2 ) H 3 O +
P h 3 P +
C R 2 –
1 ) R L i , 2 ) H 3 O +
1 ) N a B H 2 , 2 ) H 3 O +
N2H4 , KOH
a m i n e , N
a B H 3 C N
R 2 N H
R N H 2
Zn (Hg), HCl
P t , H 2
hemiacetals
,-unsaturatedesters
-haloketones -hydroxyalkynes cyanohydrins
alkanes
imines
enamines
amines
1) NaCN2) H2O(MeO)2P
1)
2) Base
CH2C
O
OEt
O
R2CuLivinyl halides
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ROADMAP FOR REACTIONS
Key:
Chapter 15
Carbon-carbon bond forming
reactions are indicated by
reagents written with solid
backgrounds and white lettering.
Chapter 16
Chapter 17
Chapters 15 16 17
H 3 O + / H 2 O
B r 2 , a c i d
H3O+ /H2O
S O C l 2
CH2N2
1) LiAlH4 , 2) H3O+ /H2O
ROH acid
R O H / H +
ROH/H+
cyclopropanes
geminal dihalocyclopropanes
acetals
aldehydes/ ketones
alkenes
carboxylicacids
esters
haloalkanes
acid chlorides
alcohols
CHX3
(CH3)3COK
1) Mg, 2) , 3) H3O+ /H
2O
CH2I2
Zn (Cu)
1) RC2) H3O+ /H2O
CNa
1) Mg
2) CO2
3) H3O+ /H2O
R2CuLi
O
1 ) R M g X ,
2 ) H 3 O +
P h 3 P +
C R 2 –
1 ) R L i , 2 ) H 3 O +
1 ) N a B H 2 ,
2 ) H 3 O +
N2H4 , KOH
a m i n e , N
a B H 3 C N
R 2 N H
R N H 2
Zn (Hg), HCl
P t , H 2
hemiacetals
,-unsaturatedesters
-haloketones -hydroxyalkynes cyanohydrins
alkanes
imines
enamines
amines
1) NaCN2) H2O(MeO)2P
1)
2) Base
CH2C
O
OEt
O
vinyl halides
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ROADMAP FOR REACTIONS
Key:
Chapter 15
Carbon-carbon bond forming
reactions are indicated by
reagents written with solid
backgrounds and white lettering.
Chapter 16
Chapter 17
Chapter 18
Chapters 15 16 17 18
H 3 O + / H 2 O
B r 2 , a c i d
H3O+ /H2O
S O C l 2
CH2N2
1) LiAlH4 , 2) H3O+ /H2O
1) LiAlH4 , 2) H3O+ /H2O
1) LiAlH4 , 2) H3O+ /H2O
1 ) L i A l H 4 , 2 ) H 3 O + / H 2 O
1 ) D I B A L , 2 ) H 3 O +
H2O acid or base
H2O acid or base
H2O acid or base
ROH acid
RCO2H
H 2 O
H2O ROH
ROH
R O H / H +
ROH/H+
cyclopropanes
geminal dihalocyclopropanes
acetals
aldehydes/ ketones
alkenes
carboxylicacids
esters
haloalkanes
acid chloridesNHR2
NHR2
N H R 2
acidanhydrides
nitriles
amides
alcohols
CHX3
(CH3)3COK
1) Mg, 2) , 3) H3O+ /H
2O
CH2I2
Zn (Cu)
1) RC2) H3O+ /H2O
CNa
1) Mg
2) CO2
3) H3O+ /H2O
R2CuLi
O
1 ) R M g X , 2 ) H 3 O +
1 ) R 2 C u L i , 2 ) H 2 O
1 ) 2 R M g X , 2 ) H 2 O
P h 3 P +
C R 2 –
1 ) R L i , 2 ) H 3 O +
1 ) N a B H 2 , 2 ) H 3 O +
N2H4 , KOH
a m i n e , N
a B H 3 C N
R 2 N H
R N H 2
Zn (Hg), HCl
P t , H 2
hemiacetals
,-unsaturatedesters
-haloketones -hydroxyalkynes cyanohydrins
alkanes
imines
enamines
amines
1) NaCN2) H2O(MeO)2P
1)
2) Base
CH2C
O
OEt
O
vinyl halides
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Carbon-carbon bond forming
reactions are indicated by
reagents written with solid
backgrounds and white lettering.
ROADMAP FOR REACTIONS
H3O+R3
R2
R1O
R4HONaOR/HOR
Aldol Reaction
various enolatesor amines
Michael Reaction
1) R2CuLi2) H3O+ /H2O
1) 2°-amine2) acid chloride3) H3O+ /H2O
1) NaOEt/HOEt2) H3O+ /H2O
1) LDA2) R-X3) H3O+ /H2O
1) 2°-amine2) R-X
3) H3O+ /H2O
ketones,aldehydes
-Hydroxy carbonyls
ClaisenCondensation
esters
-ketoesters
1) NaOEt/HOEt2) H3O+ /H2O
R4 R5
R3
R1
R6
R7
R8R2
OO
O
DieckmannCondensation
diesters
cyclic -ketoesters
1) NaOEt/HOEt2) R-X3) NaOH, H2O4) H3O+ /H2O5)
1) NaOEt/HOEt2) R-X3) NaOH, H2O4) H3O+ /H2O5)
Malonic Ester Synthesis
malonicesters
alkylated carboxylic acids
Acetoacetic Ester Sythesis
acetoaceticesters
alylated methyl ketones
R3R2
R1
O
R4
O
OH
OH
R1
O
R1
R2
O
H3C
H3C
R1
O
R1
R2
Alkylated -carbons
R3
R2
R1
O
R4
,-Unsaturated carbonyls
-Alkylated carbonyls
R2
R3
R4
R1
O
Nu
Nu = enolate formingspecies or amines
R2
R3
R4
R1 R5
O
Chapter 19
R2 R3
R1 R4
O O
R2 R3
OR4R1
O O
-Dicarbonyls
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ROADMAP FOR REACTIONS
Carbon-carbon bond forming
reactions are indicated by reagents
written with solid backgrounds
and white lettering.
HX
alkene
dienes
cyclohexenes
allylic halides
Chapter 20
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ROADMAP FOR REACTIONS
H2CrO4
H2CrO4NBS
carboxyphenols
quinones
aryl carboxylicacids
benzylicbromides
Chapter 20
Key:Carbon-carbon bond forming
reactions are indicated by reagents
written with solid backgrounds
and white lettering.
Chapter 21
HX
alkene
dienes
cyclohexenes
allylic halides
Chapters 20 21
alkylbenzenes
phenols1) NaOH2) CO2
3) H3O+ /H2O
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ROADMAP FOR REACTIONS
H2CrO4
H2CrO4NBS
N a O H , H 2 O
H 2 , N i
HNO3 , H2SO4
H2SO4 , SO3
1
) F e , H C l
2
) N a O H
phenols
carboxy
phenols
quinones
anilines
nitrobenzenes
aryl carboxylicacids
benzylicbromides
1) NaOH2) CO2
3) H3O+ /H2O
Chapter 20
Key:Carbon-carbon bond forming
reactions are indicated by reagents
written with solid backgrounds
and white lettering.
Chapter 21
Chapter 22
sulfobenzenes
acyl benzenes
aryl rings
HX
alkene
R(CO)X, AlX3
dienes
cyclohexenes
allylic halides
Chapters 20 21 22
R X , A l
X 3
3 ° - R O H , H
3 P O 4
H3PO4
NaNH2 , NH3
X2 , FeX3
alkylbenzenes
halobenzenes
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ROADMAP FOR REACTIONS
H2O
H2CrO4
H2CrO4NBS
N a O H , H 2 O
H 2 , N i
HNO3 , H2SO4
H2SO4 , SO3
1 ) F e , H C l
2 ) N a O H
phenols
carboxyphenols
quinones
H 3 P O 2
1) HNO2 , 2) HClanilines
nitrobenzenes
alkylbenzenes
aryl carboxylicacids
benzylicbromides
halobenzenes
1) KN3 ,2) H2O,3) LiAlH4 ,4) H3O+ /H2O
1) NaOH2) CO2
3) H3O+ /H2O
1 ) e x c e s s M e l
2 ) N a O H , h e a t
1 ) H 2 O 2 , 2 ) h e a t
Chapter 20Key:
Carbon-carbon bond forming
reactions are indicated by reagents
written with solid backgrounds
and white lettering.
Chapter 21
Chapter 22
Chapter 23
epoxides
H B F 4
vicinal aminoalcohols
aryl fluorides
aryl nitriles
sulfobenzenes
acyl benzenes
KIaryl iodides
aryl rings
ketones
HX
alkene
KCN, CaCN
R(CO)X, AlX3
dienes
aryldiazonium
salts
cyclohexenes
amines
alkenes
allylic halides
Chapters 20 21 22 23
R X , A l X 3
3 ° - R O H , H 3 P O 4
H3PO4
HNO2
NaNH2 , NH3
X2 , FeX3