Reaction Summary

Nucleophilic substitution: alkyl-leaving group ! alkyl-nucleophile

Nucleophile
LG

Aprotic polar
solvent
Concerted reaction (SN2)

Nucleophile
Nu

Nu
Protic
solvent
Via carbocation intermediate (SN1)
LG

Elimination: alkyl-leaving group ! alkene

Strong base
LG

H2SO4

OH

heat

Concerted reaction (E2)

heat

Via carbocation intermediate (E1)

Halogen addition: alkene ! vicinal dihaloalkane or halohydrin

OH

Br2

Br2

H2O

CH2Cl2

Anti addition
(cyclic
bromonium
ion)

Br

Br

Br

ROH addition: alkene ! alcohol or ether

OH

H2SO4

R
H2SO4

Markovnikov
addition
(no stereochem
constraints)

Markovnikov
addition
(Anti addition)

H2O

ROH
Via carbocation intermediate
Oxymercuration/reduction: alkene ! alcohol or ether
OH 1. Hg(OAc) / H O
2
2
2. NaBH4

1. Hg(OAc)2 / ROH

2. NaBH4

Hydroboration/oxidation: alkene ! alcohol

1. BH3

Anti-Markovnikov
addition
(Syn addition)

OH

2. NaOH/H2O2
Ozonolysis: alkene ! carboxylic acids or aldehydes
OH
O O

OH
H

1. O3

1. O3

2. H2O2

2. (CH3)2S

H
O O

Tosylate synthesis: alcohol ! tosylate

Tosyl chloride O
(TsCl)
Cl S
CH3

R-OTs
O

OH

O S

CH3

Pyridine
Alkyl halide synthesis: alcohol ! alkyl halide
Br

PBr3

OH

Cl

SOCl2
Pyridine

Alcohol oxidation: alcohol ! aldehyde

(PCC)

OH

CrO3

Pyridine

Alcohol oxidation: alcohol ! carboxylic acid or ketone

OH

K2Cr2O7

OH

K2Cr2O7

OH
Glycol oxidation: glycol ! aldehyde and/or ketone
HO

OH

H5IO6

Nucleophilic substitution: alkyl-leaving group ! alcohol

O
NaOH/H2O
O
CH3
LG
Aprotic polar
solvent
O
CH3
Concerted reaction (SN2)
O

For secondary
substrates
OH

Hydrogenation: alkene ! alkane

H2
Pd/C
Hydrogenation: alkyne ! alkane
H2
Pd/C
Hydrogenation: alkyne ! alkene
trans

cis

Na

H2

NH3

Lindlar

Hydrogenation: aromatic ! aromatic or to alkane

H2

H2

Pd/C

Glycol synthesis: alkene ! glycol

OsO4

Pt, high pressure

HO

OH
Syn addition

H2O/t-butyl alcohol
pyridine/TMAO

Epoxide synthesis: alkene ! epoxide

O
m-chloroperoxy- Cl
OH
benzoic
O
acid
(MCPBA)
O
Syn addition

Epoxide synthesis: halohydrin ! epoxide

Br

NaOH (1 equiv)
O
OH

SN2 attack by hydroxyl

on carbon with Br

Epoxide ring-opening (basic): epoxide ! alcohol and nucleophile

O

OH

1. Nucleophile (basic conditions)

2. Protonate product

Nu

(Example: if the nucleophile is

an alcoxide (RO), the result
is an alcohol/ether; note that
the nucleophile is on the
less substituted carbon.)

Epoxide ring-opening (acidic): epoxide ! alcohol and nucleophile

O

Nu

Nucleophile
H2SO4

OH

(Example: if the nucleophile is

an alcohol, the result
is an alcohol/ether); note that
the nucleophile is on the
more substituted carbon.)

Epoxide ring-opening (Grignard) epoxide ! alcohol two carbons longer

O
Oxirane

1. R-Mg-Br
2. Protonate product

OH

Note: this only yields

predictable product
when using oxirane)

HX addition: alkyne ! vinyl halide

Note: excess HBr will
result in geminal dibromide
following second HBr addition

HBr
Br
Hydration: alkyne ! ketone
Hg2+/H2O

Markovnikov addition
followed by enol/keto
tautomerization

Hydroboration/oxidation: alkyne ! aldehyde

1. BH(amyl)2
2. NaOH/H2O2

O
H

Grignard synthesis: alkyne ! Grignard reagent

CH3CH2MgBr
MgBr
ether
Grignard synthesis: haloalkane ! Grignard reagent
Mg
R Br
R MgBr
ether

Anti-Markovnikov
addition
(Syn addition)
followed by
enol/keto
tautomerization

EAS Nitration: aromatic ! nitro-aromatic

NO2

HNO3
H2SO4

EAS Halogenation: aromatic ! halo-aromatic

X

X2
FeX3 (X= Cl, Br, I)

Friedel-Crafts Alkylation: aromatic ! alkyl-aromatic

R
R
R
+ others R

R-Cl
AlCl3

H2SO4

R
+ others

Friedel-Crafts Acylation: aromatic ! acyl-aromatic

O
O
R

Cl

AlCl3
EAS Sulfonation: aromatic ! aromatic sulfonic acid
SO3H

SO3
H2SO4
Benzylic/allylic bromination
O
CH3

N
Br

Br

O
NBS

CH2

Benzylic oxidation: alkyl-aromatic ! aromatic carboxylic acid

O
R

KMnO4

OH

Nucleophilic aromatic substitution: aryl halide ! aryl-nucleophile

Note: at least
X Nucleophile
Nu
one activating group in
ortho or para position is
necessry
A
A