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Roadmap for Reactions of Alkanes, Alkenes, Alkynes, Alcohols & Ethers

Carbon-carbon bond forming reactions are indicated by reagents written with solid backgrounds. Reactions that cleave carbon-carbon bonds are
indicated by reagents that are circled.
vicinal tetrahaloalkanes

Legend on the next page.


2

alkynes

3) S
2

CH
2)(
O

vicinal
dihaloalkanes

r Cat

1) LiAlH4, 2) H2O

(J)
id
ac

alkyl azides
halohydrins

2O

vicinal diols

H O+
3
/H

X2, hv or heat (H)


)

alkanes

BPA

m-C

i (D

rN

O (B
X 2/H 2

t, o

d, P

(I
3
aN

amines

O
, H 2 , H 2O
Cl 2
1) aOH
N
2)

(I)

/P
H2

R2

NH

(E

R,

NaOR (K)

R
O
Na

haloakanes
NaCN (I)

silyl ethers
ethers

D)
sO 4 (
1) O
HSO 3
2) Na

(I)

HX (A)

SR

nitriles

)
NaC

Na

ROH/acid (J)

HBr, peroxides (C)

thioethers

Ni

alkenes

HO

(I

CR (E

aS

l2 (
L)

OC

.(F)

H2 /Pd, Pt,

thiols

NaO
H(
E)
HO
2 ,a
cid (
J)

X2 (B)

Cl
Si
e3
uM ine
t -B yrid
p

(G)

indla

S(

carboxylic
acids

alcohols

HX
o
rP
Br
or S

NB

H 2/L

Na/NH 3

allylic halides

M)

(
rO 4
H 2C

3,

,
O2
H2
,3 2) D)
BH (C,
1)
OH
Na
)
(A
4
)
H
(A
aB
O
)N
2
2
H
,
+/
O
O
2
,H
H3
2
)
Ac
4
O
PO
g(
H3
H
1)

1)

geminal
dihaloalkanes

aldehydes/ketones

HIO4

(A)

NaNH2/NH3

HX

1)BH 3 NaOH
,
2)H 2O 2
A)
O (
HgS 4
,
O
4
H 2S

PCC (M)

i (E)
RC C L

H2CrO4 (N)

2X

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

epoxides

NH3

vicinal
aminoalcohols

(A) Regiochemistry: Markovnikov addition to a p bond


(B) Stereochemistry: anti-addition
(C) Regiochemistry: non-Markovnikov addition to a p bond
(D) Stereochemistry: syn-addition
(E) Works well for methyl and 1 haloalkanes
(F) Stereochemistry: gives cis-alkenes as products
(G) Stereochemistry: gives trans-alkenes as products
(H) Reactivity of C-H bonds follows 3 > 2 > 1
(I) Works for methyl, 1, and 2 haloalkanes
(J) Works for 2 and 3 haloalkanes, may see rearrangements
(K) Works for all haloalkanes except methyl, although a bulky (non-nucleophilic)
base must be used for 1 haloalkanes. Regiochemistry: follows Zaitzevs rule so
the more substituted alkene predominates. Stereochemistry: requirement for
the X and H to be eliminated with anti-periplanar geometry.
(L) PBr 3 and SOX 2 works for methyl, 1, and 2 Haloalkanes. HX can give
rearrangements.
(M) For 1 alcohols.
(N) For 2 alcohols.
(O) Regiochemistry: the product with the more substituted alkene predominates.

Roadmap for Reactions of Carbonyl Compunds, Carboxylic acids & Derivatives

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

O
O
1)(MeO)2P CH2C OEt
2) Base

a,b-unsaturated esters

Br

2,

imines

ac

ROH/H+

hemiacetals
+

ROH/H

amine,

aldehydes/
ketones

H3O+/H2O

H3O+/H2O

enamines

H
R 2N

RNH2

id

NaBH 3C

1) NaCN
2) H2O

O
3
)H

acetals

,2

Cl

3O +

)H
L, 2
IBA

alkanes

haloalkanes

CH2I2
Zn (Cu)

(R

iAlH

4,

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

1) L

CHX3
(CH3)3COK

uL
i

alkenes
2C

1) 2R

2) H

Ph3P+2CR2

1) D

3O +

, 2) H

2O

/H

HO
2
3 O +/

3O +

H
2)
4,

lH
LiA
1)

MgX

2O

)H
i, 2
uL
2C

R
1)

3) H3O+/H2O

a-hydroxyalkynes

O
,K
H4
N2

1) Mg
O
2)

1) RC CNa
2) H3O+, H2O

H
),

alcohols

2
H2
aB
2
N
,H
1)
Pt

g
(H

1)

O
3
)H

,2
Li

Zn

1)

cyanohydrins

O
3
)H

gX

RM

geminal dihalo
cyclopropanes

vinyl halides
cyclopropanes

carboxylic acids
H
RO

id
s
ba
or

ac

SOCl

O
H2

esters
ROH

acid chlorides

H 2O

N
CH 2

H 2O

H2O

acid

O
H2
d
aci ase
b
or

RCO H
2

RO

NHR

acid anhydrides

NHR2

amides

NHR2
HO
2
acid
o

r ba

se

nitriles

amines

+ H O
/ 2
, 2) H 3O
1) LiAlH 4

1) LiAlH4
2) H3O+/ H2O

amines

Roadmap for Reaction of Enolate Anions and Enamines


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

R2

R2

R1

R5
R4

R1

O
Nu

R4
O
R3
Nu = enolate forming
species or amines

O
R3
-Alkylated carbonyls

1) R2CuLi
2) H3O+/H2O

Michael
Reaction

Various enolates
or amines

R1

O
R2

R8

R7

R6
R4 R5
Cyclic -Ketoesters
R3

Dieckmann
Condensation

1) NaOEt
HOEt
2) H3O+/H2O

diesters
R3

R3
R4

HO
R1

R1

H3O+

O
R2
-Hydroxy carbonyls

O
R2
-Unsaturated carbonyls

NaOR
HOR

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

R2
Alkylated -carbons

R1

OR4
O
O
-Ketoesters

Enamine
Reactions

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

R4
R3

R1

R2 R3

Aldol
Reaction
ketones,
aldehydes

R4

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

Claisen
Condensation

ester
O
R1

O
R4

R1

HO

R2 R3
-Dicarbonyls

O
HO

O
O
H3C

R1

R2
Alkylated methyl ketones

R1

R2
Alkylated carboxylic acids

R1

H3C

1) NaOEt
HOEt
2) H3O+/H2O

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

Malonic Ester
Synthesis
acetoacetic
ester

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

malonic ester

Roadmap for Reactions of Benzene & Its Derivatives and Amines

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

dienes

cyclohexenes

HX

allylic halides

amines
1) excess Mel
2) NaOH, heat

alkenes

epoxides

1) H2O2
2) heat

1) KN3
2) H2O

3) LiAlH4
4) H3O+/H2O

vicinal amino
alcohols
HNO2

aryl
nitriles

aryl flourides
ketones

aryl iodides

HBF4

KCN
CaCN

quinones

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

KI

aryl diazonium
salts

H2CrO4

1) HNO2
2) HCl

aryl
carboxylic acids

H2O

benzylic bromides

NaOH
H2O

H2CrO4

anilines

H3PO2

phenols

NaNH2
NH3

NBS

alkyl benzenes
halobenzenes
RX
AlX3
H3PO4
R(CO)X
AlX3

acyl benzenes

X2, FeX3

3-ROH
H3PO4

aryl rings

HNO3
H2SO4
H2SO4
SO3

sulfobenzenes

nitrobenzenes

1) Fe
HCl
2) NaOH

H2, Ni

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