Typical

Conditions

Notes [1, 2 and 3 refers to

primary, secondary, tertiary]

Free radical chlorination

Cl2, h

Not highly selective

Free radical bromination

Br 2, h

Highly selective for tertiary CH

Elimination [E2]

RO /ROH

Best for 2 and 3, anti stereochemistry

Elimination [E1]

polar solvent,
heat

Competes with SN1

Alcohol Formation [SN2]

Alcohol Formation [SN1]

"Solvolysis"

Reaction

Reaction Map: Reactions of Alkanes, Alkyl Halides, Alkenes, Alkynes and Alcohols

56

Alkenyl halides
X
H
R

Vicinal
Dihalides
X
X

Geminal
Dihalides
X
X
R

51

50

54

55

55

23
21

53

24
20

52
Alkenyl dihalides

Epoxides
O

27

47

28

39

R C C R

40

29
42

38

15

30

44

SN2; best for 1 alkyl halides, 2 OK

10

Sulfide formation [SN2]

SR

SN2; best for 1 alkyl halides, 2 OK

11

Ester formation [SN2]

12

Azide formation [SN2]

N3

SN2; best for 1 alkyl halides, 2 OK

13

Nitrile formation [SN2]

CN

SN2; best for 1 alkyl halides, 2 OK

14

Alkyne formation [SN2]

15

Addition of H-Cl To Alkenes

HCl

Markovnikov-selective; rearr. possible

65

16

Addition of H-Br To Alkenes

HBr

Markovnikov-selective; rearr. possible

Thiols

17

Addition of H-I To Alkenes

HI

Markovnikov-selective; rearr. possible

18

Radical addition of HBr to

alkenes

HBr, h

anti-Markovnikov-selective; radical process

19

Hydrogenation of alkenes

Pd/C, H 2

syn- selective

20

Alkene chlorination

Cl2, CCl4

anti- selective

21

Alkene bromination

Br 2, CCl4

anti- selective

22

Alkene iodination

I 2, CCl4

anti- selective

23

Chlorohydrin formation

Cl2, H 2O

anti- selective; Markovnikov selective, water

is solvent. Alcohol solvent gives ether

Br 2, H 2O

anti- selective; Markovnikov selective, water

is solvent. Alcohol solvent gives ether

Ring opened
products
HO

60

58

18
68

67

Nu

Disulfides
R S S R

61

"Carbonyls"
66

62

O
O

SH

R OH

17

HO

ROH

Best for 1 alkyl halides; 2 can compete w/ E2

Best for 3 alkyl halides; rearr possible w/ 2

RCO 2

in
polar
aprotic
solvent

SN2; best for 1 alkyl halides, 2 OK

Alcohols

16

31

Ether Formation [SN2]

RO /ROH
["Williamson Ether Synthesis"]

Thiol formation [SN2]

19

43
Tetrahalides
X
X
X
X
R
R

37

Best for 3 alkyl halides; rearr possible w/ 2

R OR
59

36

H 2O

46
45

35

Best for 1 alkyl halides; 2 can compete w/ E2

Ether Formation [SN1]

"Solvolysis"

Ethers
34

OH / H 2O

69

25

Alkenes

Alkynes

26

32

41
47

OH

22

48

Cyclopropanes

33

49

HO

57

Vicinal Diols

Halohydrins
HO
X

Name

O
4

Alkanes
RH

63

64

R SH

1
2

Alkyl Halides

10

RX

R C C

Best for 1 alkyl halides; 2 can compete w/ E2

14
Alkyl Sulfonates
This "map" includes reactions typically covered in chapters covering:
Substitution and eliimination reactions of alkyl halides
Reactions of alkenes
Reactions of alkynes
Free-radical substitution of alkanes
Alcohols and thiols

10

11
13

12

It will be expanded as subsequent chapters are covered

Please feel free to add comments or sugestions!

Sulfides
["Thioethers"]
R SR

ROTs
ROMs

or NCS

Esters
Nitriles
R C N

Azides
R N3

O
R O
R

24

Bromohydrin formation

or NBS

25

Iodohydrin formation

Cl2, H 2O
or NIS

26

Epoxidation of alkenes

27

Dihydroxylation of alkenes
with OsO 4

RCO 3H
(e.g. m-CPBA)
OsO 4, KHSO 3

anti- selective; Markovnikov selective, water

is solvent. Alcohol solvent gives ether
anti- selective; Markovnikov selective, water
is solvent. Alcohol solvent gives ether
syn- selective. KHSO 3 helps remove Os

(e.g. m-CPBA)
syn- selective. Important to keep cold,
otherwise oxidative cleavage occurs (see 31)

28

Dihydroxylation of alkenes
(cold KMnO 4)

KMnO 4, NaOH
(cold, dilute)

29

Ozonolysis (reductive
workup)

O 3, then Zn/H+ or cleaves C=C to give two carbonyls. Alkenyl

C-H bonds remain
(CH3)2S

30

Ozonolysis (oxidative
workup)

O 3, then H 2O 2

cleaves C=C to give two carbonyls. Alkenyl

C-H bonds oxidized to COH

31

Oxidative cleavage with

KMnO 4

KMnO 4, acid,
heat

cleaves C=C to give two carbonyls. Alkenyl

C-H bonds oxidized to COH

32

Cyclopropanation (SimmonsSmith)

Cu/Zn, CH2I 2

syn-selective

33

Dichlorocyclopropanation

CHCl3, KOH

syn-selective

56

Formation of epoxides from

halohydrins

NaH (strong
base)

Internal SN2 reaction: inversion of

configuration at carbon

57

Opening of epoxides with

aqueous acid

H 3O+ (or
H 2O/H 2SO4 )

Protonation of epoxide, then attack of H 2O at

most substituted carbon

58

Elimination of alcohols to
form alkenes (acidic)

H 2SO4, heat

Follows Zaitsev's rule (most sub. alkene

formed). Rearrangements can occur

59

POCl 3 elimination of
alcohols to alkenes

POCl 3,
pyridine

E2 reaction

34

Acid-catalyzed ether
formation

H 2SO4, ROH

Markovnikov selective, rearr. possible

35

Oxymercuration

Hg(OAc) 2, ROH,
then NaBH 4

Markovnikov selective, alcohol is solvent

36

Oxymercuration

Hg(OAc) 2, H 2O,
then NaBH 4

Markovnikov selective, water is solvent

60

Acidic cleavage of ethers

HI, heat

Can proceed through SN2 or SN1 depending

on type of alcohol

37

Hydroboration

BH 3, then NaOH,
H 2O 2

anti-Markovnikov selective, syn-selective

61

Conversion of alcohols to
alkyl halides with PBr 3

PBr 3

SN2 reaction. PCl 3 can also be used to make

alkyl chlorides

38

Acid-catalyzed hydration

H 2SO4, H 2O
("H3O+")

Markovnikov selective; rearr possible

62

SOCl2 conversion of
alcohols to alkyl chlorides

SOCl2

Usually taught as SN2. Pyridine can be used

as base.

39

Partial hydrogenation
(Lindlar)

Lindlar, H 2

syn-selective
63

HCl, HBr, HI

40

Partial hydrogenation
(sodium reduction)

Na/NH 3

anti-selective

Alcohols to alkyl halides

with HX

Can go through SN1 or SN2 depending on

type of alcohol

Alkyne hydroboration

BH 3, then NaOH,
H 2O 2

anti-Markovnikov selective; tautomerization

64

Tosylate and mesylate

formation

TsCl or MsCl

41

Does not affect stereochemistry. Can use a

base such as pyridine.

42

Alkyne Oxymercuration

HgSO 4, H 2O,
H 2SO4

Markovnikov selective; tautomerization

65

Disulfide formation

I 2 (oxidant)

Can use other oxidants but I 2 is most

common

43

Alkyne Ozonolysis

O3

Carboxylic acids formed; terminal alkynes

give CO2

66

Alcohol oxidation with PCC

PCC

1 alcohols to aldehydes; 2 alcohols to

ketones

44

Alkyne Ox. Cleavage

[KMnO 4]

KMnO 4, H +

same as ozonolysis

67

Alcohol oxidation with

H 2CrO4

K 2Cr2O 7 +
acid

1 alcohols to carboxylic acids, 2 alcohols

to ketones.

45

Hydrogenation

Pd/C, H 2

Adds twice to alkynes

68

Dess Martin oxidation

Dess Martin
Periodinane

1 alcohols to aldehydes; 2 alcohols to

ketones

46

Alkyne double halogenation

Cl2, Br 2, or I 2
(2 equiv)

Each individual reaction is anti-selective

69

Basic ring opening of

epoxides

Grignards,
OH, LiAlH
4

Add to least substituted position of epoxides

47

Halogenation

Cl2, Br 2, or I 2
(1 equiv)

anti-selective

48

Addition of HCl to Alkynes

HCl

Markovnikov selective

49

Addition of HBr to Alkynes

HBr

Markovnikov selective

50

Addition of HI to Alkynes

HI

Markovnikov selective

51

Addition of HX to
haloalkenes

HCl, HBr,
or HI

Markovnikov selective

52

Double addition of HCl to

Alkynes

HCl [2 equiv]

Adds twice to alkyne; Markovnikov selective

53

Double addition of HBr to

Alkynes

HBr [2 equiv]

Adds twice to alkyne; Markovnikov selective

54

Double addition of HI to
Alkynes

HI [2 equiv]

Adds twice to alkyne; Markovnikov selective

55

Elimination of dihalides to
give alkynes

NaNH 2 [2
equiv]

vicinal or geminal dihalides; for terminal

alkynes, 3 equiv NaNH 2 required