ROADMAP FOR REACTIONS

aldehydes/
ketones

vicinal
dihaloalkanes

halohydrins
1) O3, 2) (CH3)2S
1) OsO4 (D), 2) NaHSO3
X2 (B)

(M)
(N)
(O)

Reactions that cleave carbon-carbon

bonds are indicated by reagents
that are circled.

vicinal
diols

1) BH3, 2) H2O2, NaOH (C, D)

alkanes

H2/Pd, Pt,or Ni (D)

alkenes

HX (A)

(L)

Regiochemistry: Markovnikov addition to a P bond

Stereochemistry: anti-addition
Regiochemistry: non-Markovnikov addition to a V bond
Stereochemistry: syn-addition
Works well for methyl and 1 haloalkanes
Stereochemistry: gives cis-alkenes as products
Stereochemistry: gives trans-alkenes as products
Reactivity of CH 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 Zaitzevs 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

X2/H2O (B)

(A)
(B)
(C)
(D)
(E)
(F)
(G)
(H)
(I)
(J)
(K)

Chapter 6

haloakanes

H3O+/H2O (A)
1) Hg(OAc)2, H2O, 2) NaBH4, (A)

alcohols

ROADMAP FOR REACTIONS

Chapters 6 7
Key:

Carbon-carbon bond forming

reactions are indicated by reagents
written with solid backgrounds
and white lettering.

Chapter 6
Chapter 7

vicinal
tetrahaloalkanes

geminal
dihaloalkanes

HX (A)

Reactions that cleave carbon-carbon

bonds are indicated by reagents
that are circled.

2X2

1) (sia)2BH, 2) H2O2, NaOH (C)

1) BH3, 2) H2O2, NaOH

alkynes

aldehydes/
ketones

H2 /Lindlar Cat. (F)

Na /NH3 (G)

H2 /Pd, Pt, Ni

vicinal
dihaloalkanes

halohydrins
1) O3, 2) (CH3)2S

X2 (B)

1) OsO4 (D), 2) NaHSO3

X2/H2O (B)

vicinal
diols

1) BH3, 2) H2O2, NaOH (C, D)

alkanes

H2/Pd, Pt,or Ni (D)

alkenes

HX (A)

NaC

CR (E)

NaNH2 /NH3

H2SO4, HgSO4 (A)

haloakanes

H3O+/H2O (A)
1) Hg(OAc)2, H2O, 2) NaBH4, (A)

alcohols

ROADMAP FOR REACTIONS

Chapters 6 7 8
Key:
Chapter 6
Chapter 7
Chapter 8

vicinal
tetrahaloalkanes

geminal
dihaloalkanes

Reactions that cleave carbon-carbon

bonds are indicated by reagents
that are circled.

2X2

HX (A)

Carbon-carbon bond forming

reactions are indicated by reagents
written with solid backgrounds
and white lettering.

1) (sia)2BH, 2) H2O2, NaOH (C)

alkynes

1) BH3, 2) H2O2, NaOH

aldehydes/
ketones

H2 /Lindlar Cat. (F)

Na /NH3 (G)

H2 /Pd, Pt, Ni

vicinal
dihaloalkanes

halohydrins
1) O3, 2) (CH3)2S

X2 (B)

X2/H2O (B)

1) OsO4 (D), 2) NaHSO3

vicinal
diols

1) BH3, 2) H2O2, NaOH (C, D)

H3O+/H2O (A)
1) Hg(OAc)2, H2O, 2) NaBH4, (A)

alcohols

NBS (O)

allylic
halides

HX (A)

alkanes

alkenes

H2/Pd, Pt,or Ni (D)

HBr, peroxides (C)

NaC

RC

CR (E)

NaNH2 /NH3

H2SO4, HgSO4 (A)

X2, hv or heat (H)

haloakanes

(A)
(B)
(C)
(D)
(E)
(F)
(G)
(H)
(I)
(J)
(K)

(L)
(M)
(N)
(O)

Regiochemistry: Markovnikov addition to a P bond

Stereochemistry: anti-addition
Regiochemistry: non-Markovnikov addition to a V bond
Stereochemistry: syn-addition
Works well for methyl and 1 haloalkanes
Stereochemistry: gives cis-alkenes as products
Stereochemistry: gives trans-alkenes as products
Reactivity of CH 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 Zaitzevs 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

ROADMAP FOR REACTIONS

Chapters 6 7 8 9
Key:
Chapter 6
Chapter 7
Chapter 8
Chapter 9

vicinal
tetrahaloalkanes

geminal
dihaloalkanes

2X2

HX (A)

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.

1) (sia)2BH, 2) H2O2, NaOH (C)

alkynes

1) BH3, 2) H2O2, NaOH

aldehydes/
ketones

H2 /Lindlar Cat. (F)

Na /NH3 (G)

vicinal
dihaloalkanes

halohydrins
1) O3, 2) (CH3)2S

vicinal
diols

X2 (B)

X2/H2O (B)

1) OsO4 (D), 2) NaHSO3

1) BH3, 2) H2O2, NaOH (C, D)

alkanes

alkenes

H2/Pd, Pt,or Ni (D)

H3O+/H2O (A)
1) Hg(OAc)2, H2O, 2) NaBH4, (A)

alcohols

nitriles

thiols

thioethers

amines

NaN3 (I )

NaHR2 ( I )

NaSR (I )

NaSH (I )

haloakanes

alkyl
azides

H2O, acid (J)

NaOH (E)

NaOR (E)

X2, hv or heat (H)

HOR, acid (J)

ethers

NaOR (K)

allylic
halides

HX (A)

HBr, peroxides (C)

NBS (O)

NaCN (I )

CR (E)
NaC

H2 /Pd, Pt, Ni

CLi (E)
RC

NaNH2 /NH3

H2SO4, HgSO4 (A)

ROADMAP FOR REACTIONS

Chapters 6 7 8 9 10
Key:
Chapter 6

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

vicinal
tetrahaloalkanes

Chapter 10

2X2

1) (sia)2BH, 2) H2O2, NaOH (C)

alkynes

1) BH3, 2) H2O2, NaOH

aldehydes/
ketones

HIO4

H2 /Lindlar Cat. (F)

Na /NH3 (G)

vicinal
dihaloalkanes

halohydrins
1) O3, 2) (CH3)2S

vicinal
diols

X2 (B)

X2/H2O (B)

1) OsO4 (D), 2) NaHSO3

1) BH3, 2) H2O2, NaOH (C, D)

H3O+/H2O (A)

alkanes

alkenes

H2/Pd, Pt,or Ni (D)

1) Hg(OAc)2, H2O, 2) NaBH4, (A)

alcohols

H3PO4

H2CrO4

HX or PBr3 or SOCl2 (L)

H2O, acid (J)

NaOH (E)

NaOR (E)

X2, hv or heat (H)

HOR, acid (J)

ethers

NaOR (K)

allylic
halides

HX (A)

HBr, peroxides (C)

NBS (O)

nitriles

thiols

thioethers

amines

NaN3 (I )

NaHR2 (I )

NaSR (I)

NaSH (I )

haloakanes
NaCN (I )

CR (E)
NaC

H2 /Pd, Pt, Ni

CLi (E)
RC

NaNH2 /NH3

H2SO4, HgSO4 (A)

H2CrO4 (N)

HX (A)

PCC (M)

geminal
dihaloalkanes

alkyl
azides

carboxylic
acids

ROADMAP FOR REACTIONS Chapters 6 7 8 9 10 11

Key:

Carbon-carbon bond forming

reactions are indicated by reagents
written with solid backgrounds
and white lettering.

Chapter 6
Chapter 7
Chapter 8
Chapter 9

vicinal
tetrahaloalkanes

Chapter 11

2X2

1) (sia)2BH, 2) H2O2, NaOH (C)

alkynes

1) BH3, 2) H2O2, NaOH

aldehydes/
ketones

HIO4

H2 /Lindlar Cat. (F)

Na /NH3 (G)

H2 /Pd, Pt, Ni

vicinal
dihaloalkanes

vicinal
aminoalcohols

halohydrins

H3O+/H2O

vicinal
diols

1) Cl2, H2O, 2) NaOH, H2O

epoxides

m-CBPA
1) BH3, 2) H2O2, NaOH (C, D)
H3O+/H2O (A)

alkenes

H2/Pd, Pt,or Ni (D)

alcohols

1) Hg(OAc)2, H2O, 2) NaBH4, (A)

H3PO4

H2CrO4

HX or PBr3 or SOCl2 (L)

H2O, acid (J)

NaOH (E)

HOR, acid (J)

HI

X2, hv or heat (H)

ethers

NaOR (E)

NaOR (K)

allylic
halides

ROH/acid (J)
HX (A)

HBr, peroxides (C)

NBS (O)

nitriles

thiols

thioethers

amines

NaN3 (I )

NaHR2 (I )

NaSR (I)

NaSH (I )

haloakanes

alkyl
azides

carboxylic
acids

t-BuMe3SiCl/pyridine

alkanes

1) LiAlH4
2) H2O

X2 (B)

X2/H2O (B)

1) OsO4 (D), 2) NaHSO3

NH3

1) O3, 2) (CH3)2S

NaCN (I )

CR (E)
NaC

RC

CLi (E)

NaNH2 /NH3

H2SO4, HgSO4 (A)

H2CrO4 (N)

HX (A)

Reactions that cleave carbon-carbon

bonds are indicated by reagents
that are circled.

Chapter 10

PCC (M)

geminal
dihaloalkanes

silyl
ethers

Chapter 15

ROADMAP FOR REACTIONS

Carbon-carbon bond forming

reactions are indicated by
reagents written with solid
backgrounds and white lettering.

geminal dihalo
cyclopropanes

CHX3
(CH3)3COK

cyclopropanes

CH2I2
Zn (Cu)

vinyl halides

R2CuLi

haloalkanes

(A)
(B)
(C)
(D)
(E)
(F)
(G)
(H)
(I)
(J)
(K)

(L)
(M)
(N)
(O)

Regiochemistry: Markovnikov addition to a P bond

Stereochemistry: anti-addition
Regiochemistry: non-Markovnikov addition to a V bond
Stereochemistry: syn-addition
Works well for methyl and 1 haloalkanes
Stereochemistry: gives cis-alkenes as products
Stereochemistry: gives trans-alkenes as products
Reactivity of CH 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 Zaitzevs 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

1) Mg, 2)

alkenes

, 3) H3O+/H2O

alcohols

Chapters 15 16

ROADMAP FOR REACTIONS

Carbon-carbon bond forming

reactions are indicated by
reagents written with solid
backgrounds and white lettering.

G,H-unsaturated
esters

acetals

G-haloketones

G-hydroxyalkynes

Key:

cyanohydrins

Chapter 15

(MeO)2P
2) Base

CH2C

1)

OEt

Br2, acid

ROH/H+

H3O+/H2O

Chapter 16
1) NaCN
2) H2O

1) RC CNa
2) H3O+/H2O

Zn (Hg), HCl

R2CuLi

haloalkanes

RNH2
Pt, H2

vinyl halides

alkenes

1) NaBH2, 2) H3O+

CH2I2
Zn (Cu)

1) RLi, 2) H3O+

cyclopropanes

1) RMgX, 2) H3O+

CHX3
(CH3)3COK

Ph3P +

geminal dihalo
cyclopropanes

imines

amine, NaBH3CN

H3O+/H2O

alkanes

N2H4 , KOH

R2NH

aldehydes/
ketones

CR2

hemiacetals

ROH/H+

enamines

amines

1) Mg, 2)

, 3) H3O+/H2O

alcohols

ROADMAP FOR REACTIONS Chapters

15 16 17
Carbon-carbon bond forming
reactions are indicated by
reagents written with solid
backgrounds and white lettering.

G,H-unsaturated
esters

acetals

G-haloketones

G-hydroxyalkynes

cyanohydrins

Key:
Chapter 15

(MeO)2P
2) Base

CH2C

Chapter 17
OEt

Br2, acid

1)

ROH/H+

H3O+/H2O

Chapter 16
1) NaCN
2) H2O

1) RC CNa
2) H3O+/H2O

Zn (Hg), HCl

R2CuLi

haloalkanes

1) Mg, 2)

RNH2

imines

Pt, H2

vinyl halides

alkenes

1) NaBH2, 2) H3O+

CH2I2
Zn (Cu)

1) RLi, 2) H3O+

cyclopropanes

1) RMgX, 2) H3O+

CHX3
(CH3)3COK

Ph3P +

geminal dihalo
cyclopropanes

enamines

amines

, 3) H3O+/H2O

alcohols

1) LiAlH4 , 2) H3O+/H2O
1) Mg
2) CO2
3) H3O+/H2O

SOCl2

carboxylic
acids

acid chlorides

amine, NaBH3CN

H3O+/H2O

alkanes

N2H4 , KOH

R2NH

aldehydes/
ketones

CR2

hemiacetals

ROH/H+

CH2N2
ROH acid

esters

ROADMAP FOR REACTIONS Chapters 15 16 17 18

Carbon-carbon bond forming
reactions are indicated by
reagents written with solid
backgrounds and white lettering.

G,H-unsaturated
esters

acetals

G-haloketones

Key:

cyanohydrins

G-hydroxyalkynes

Chapter 15

(MeO)2P
2) Base

CH2C

Chapter 17
Br2, acid

1)

ROH/H+

H3O+/H2O

Chapter 16

OEt

1) NaCN
2) H2O

1) RC CNa
2) H3O+/H2O

Chapter 18

Zn (Hg), HCl

haloalkanes

1) Mg, 2)

RNH2
1) DIBAL, 2) H3O+

R2CuLi

Pt, H2

vinyl halides

alkenes

1) NaBH2, 2) H3O+

CH2I2
Zn (Cu)

1) RLi, 2) H3O+

cyclopropanes

1) RMgX, 2) H3O+

CHX3
(CH3)3COK

Ph3P +

geminal dihalo
cyclopropanes

imines

enamines

amines

, 3) H3O+/H2O

alcohols

1) Mg
2) CO2
3) H3O+/H2O

1) 2RMgX, 2) H2O

1) LiAlH4 , 2) H3O+/H2O

H2O acid or base

CH2N2
ROH acid

carboxylic
acids

H2O

ROH

esters

NHR2

ROH

H2O

SOCl2

1) R2CuLi, 2) H2O

CR2

H3O+/H2O

alkanes

N2H4 , KOH

amine, NaBH3CN

aldehydes/
ketones

1) LiAlH4 , 2) H3O+/H2O

hemiacetals

R2NH

ROH/H+

acid chlorides

RCO2H

acid
anhydrides

NHR2

amides

1) LiAlH4 , 2) H3O+/H2O

NHR2
H2O acid or base
H2O acid or base

nitriles

1) LiAlH4 , 2) H3O+/H2O

ROADMAP FOR REACTIONS

Chapter 19
Carbon-carbon bond forming
reactions are indicated by
reagents written with solid
backgrounds and white lettering.

ketones,
aldehydes
H-Hydroxy carbonyls
Aldol Reaction
NaOR/HOR

HO H
R1

R3

H3
R4

R2

G,H-Unsaturated carbonyls
O+

R3

R1 H

R2

O
H-Alkylated carbonyls

Alkylated G-carbons

1) LDA
2) R-X
3) H3O+/H2O

O
R1

1) 2-amine
2) R-X
3) H3O+/H2O

R2

1) 2-amine
2) acid chloride
3) H3O+/H2O

R4
R3

various enolates
or amines

R4

malonic
esters

diesters

1) NaOEt/HOEt
2) H3O+/H2O

1) NaOEt/HOEt
2) H3O+/H2O

1) NaOEt/HOEt
2) R-X
3) NaOH, H2O
4) H3O+/H2O
5) 1

H-ketoesters

cyclic H-ketoesters

alkylated carboxylic acids

R1 H
O

OR4

G
O

R1

R8

OH

R7
R3

R4 R5

Nu
G H
R4
O
R3

acetoacetic
esters

1) NaOEt/HOEt
2) R-X
3) NaOH, H2O
4) H3O+/H2O
5) 1

alylated methyl ketones

O
R2

R2
R1

Acetoacetic Ester
Sythesis

Malonic Ester
Synthesis

Dieckmann
Condensation

R2 R3

R
G H 5
R4
O
R3

Nu = enolate forming
species or amines

R2 R3

esters

R1

Michael Reaction

R1

R2

1) R2CuLi
2) H3O+/H2O

H-Dicarbonyls

Claisen
Condensation

R4

R6

O
R1

O
R1

OH
R2

H3C

R1
O
R1

H3C
R2

Chapter 20

ROADMAP FOR REACTIONS

Carbon-carbon bond forming

reactions are indicated by reagents
written with solid backgrounds
and white lettering.

alkene

cyclohexenes

dienes
HX

allylic halides

Chapters 20 21

ROADMAP FOR REACTIONS

Key:

Chapter 20
Chapter 21

alkene

Carbon-carbon bond forming

reactions are indicated by reagents
written with solid backgrounds
and white lettering.

cyclohexenes

dienes
HX

quinones

benzylic
bromides

H2CrO4

NBS

allylic halides

phenols

alkyl
benzenes

1) NaOH
2) CO2
3) H3O+/H2O

carboxy
phenols

H2CrO4

aryl carboxylic
acids

Chapters 20 21 22

ROADMAP FOR REACTIONS

Key:
Chapter 20
Chapter 21
Chapter 22

alkene

Carbon-carbon bond forming

reactions are indicated by reagents
written with solid backgrounds
and white lettering.

cyclohexenes

dienes

H2CrO4

phenols

H3PO4

sulfobenzenes

aryl carboxylic
acids

H2SO4 , SO3

X2 , FeX3

aryl rings
acyl benzenes

H2CrO4

NaOH, H2O

alkyl
benzenes

carboxy
phenols

RX, AlX3

NBS

3-ROH, H3PO4

benzylic
bromides

1) NaOH
2) CO2
3) H3O+/H2O

R(CO)X, AlX3

HNO3 , H2SO4

halobenzenes

nitrobenzenes

H2 , Ni

quinones

allylic halides

1) Fe, HCl
2) NaOH

HX

anilines

NaNH2, NH3

ROADMAP FOR REACTIONS Chapters 20 21 22 23

Key:
Chapter 20
Chapter 21
alkene

Chapter 22

cyclohexenes

Chapter 23

Carbon-carbon bond forming

reactions are indicated by reagents
written with solid backgrounds
and white lettering.

dienes

1) NaOH
2) CO2
3) H3O+/H2O

phenols

H3PO4

sulfobenzenes

H2CrO4

H2SO4 , SO3

X2 , FeX3

aryl rings
R(CO)X, AlX3

HNO3 , H2SO4

H3PO2

acyl benzenes

1) HNO2 , 2) HCl

H2O

KCN, CaCN

aryl
diazonium
salts

KI

halobenzenes

nitrobenzenes

anilines

amines
1) excess Mel
2) NaOH, heat

aryl fluorides

epoxides

1) KN3 ,
2) H2O,
3) LiAlH4 ,
4) H3O+/H2O

vicinal amino
alcohols

NaNH2, NH3

aryl iodides

HBF4

aryl nitriles

aryl carboxylic
acids
NaOH, H2O

alkyl
benzenes

RX, AlX3

NBS

3-ROH, H3PO4

benzylic
bromides

carboxy
phenols

HNO2

ketones

1) H2O2 , 2) heat

H2CrO4

1) Fe, HCl
2) NaOH

quinones

allylic halides

H2 , Ni

HX

alkenes