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

Geminal Vicinal Vicinal Diols

Alkenyl halides Dihalides Dihalides Halohydrins
Cyclopropanes
X H X X X HO X HO OH
51 X
R H R R R R R Epoxides
O

55 R
50 54 55 22 23 27
33
49 21 24 26
53 28 32
48 20 25 Ethers
52
R OR
35
Alkenyl dihalides Alkynes Alkenes 34
47 39 40
R X R C C R R 36
37
X R 38
41 Alcohols
15
46 29
47 R OH
42 16
45 30
19 17
43
31
Tetrahalides 18 4 8
6
X X 44
X X 7 Thiols
3 5
R R R SH
"Carbonyls" 9
Alkyl Halides
HO Alkanes
1 2 R–X
O R–H
O 10
O Sulfides
["Thioethers"]
14 R SR
13 12 11

Esters

Nitriles O
Azides R O
R C N R N3 R
 Typical Notes [1°, 2° and 3° refers to Typical Notes [1°, 2° and 3° refers to
Reaction Name Conditions Reaction Name
primary, secondary, tertiary] Conditions primary, secondary, tertiary]
Free radical chlorination Cl2, hγ Not highly selective
1 29 Ozonolysis (reductive O3, then Zn/H+ or cleaves C=C to give two carbonyls. Alkenyl
workup) (CH3)2S C-H bonds remain
2 Free radical bromination Br2, hγ Highly selective for tertiary C–H
30 Ozonolysis (oxidative O3, then H2O2 cleaves C=C to give two carbonyls. Alkenyl
workup) C-H bonds oxidized to C–OH
3 Elimination [E2] RO /ROH Best for 2° and 3°, anti stereochemistry
31 Oxidative cleavage with KMnO4, acid, heat cleaves C=C to give two carbonyls. Alkenyl
Elimination [E1] polar solvent, Competes with SN1 KMnO4 C-H bonds oxidized to C–OH
4
heat
32 Cyclopropanation (Simmons- Cu/Zn, CH2I2 syn-selective
Alcohol Formation [SN2] OH / H2O Best for 1° alkyl halides; 2° can compete w/ E2 Smith)
5
33 Dichlorocyclopropanation CHCl3, KOH syn-selective
6 Alcohol Formation [SN1] H2O Best for 3° alkyl halides; rearr possible w/ 2°
"Solvolysis" 34 Acid-catalyzed ether H2SO4, ROH Markovnikov selective, rearr. possible
formation
7 Ether Formation [SN2] RO /ROH Best for 1° alkyl halides; 2° can compete w/ E2
["Williamson Ether Synthesis"] 35 Oxymercuration Hg(OAc)2, ROH, Markovnikov selective, alcohol is solvent
then NaBH4
8 Ether Formation [SN1] ROH Best for 3° alkyl halides; rearr possible w/ 2°
"Solvolysis" 36 Oxymercuration Hg(OAc)2, H2O, Markovnikov selective, water is solvent
then NaBH4
9 Thiol formation [SN2] SH SN2; best for 1° alkyl halides, 2° OK Hydroboration BH3, then NaOH, anti-Markovnikov selective, syn-selective
37
H2O2

10 Sulfide formation [SN2] SR SN2; best for 1° alkyl halides, 2° OK 38 Acid-catalyzed hydration H2SO4, H2O Markovnikov selective; rearr possible
("H3O+")
in
11 Ester formation [SN2] RCO2 polar SN2; best for 1° alkyl halides, 2° OK 39 Partial hydrogenation Lindlar, H2 syn-selective
aprotic (Lindlar)
solvent
Azide formation [SN2] N3 SN2; best for 1° alkyl halides, 2° OK 40 Partial hydrogenation Na/NH3 anti-selective
12 (sodium reduction)

41 Alkyne hydroboration BH3, then NaOH, anti-Markovnikov selective; tautomerization

13 Nitrile formation [SN2] CN SN2; best for 1° alkyl halides, 2° OK H2O2

42 Alkyne Oxymercuration HgSO4, H2O, Markovnikov selective; tautomerization

14 Alkyne formation [SN2] R C C Best for 1° alkyl halides; 2° can compete w/ E2 H2SO4

43 Alkyne Ozonolysis O3 Carboxylic acids formed; terminal alkynes

15 Addition of H-Cl To Alkenes H–Cl Markovnikov-selective; rearr. possible give CO2

Addition of H-Br To Alkenes H–Br Markovnikov-selective; rearr. possible 44 Alkyne Ox. Cleavage KMnO4, H+ same as ozonolysis
16
[KMnO4]

17 Addition of H-I To Alkenes H–I Markovnikov-selective; rearr. possible 45 Hydrogenation Pd/C, H2 Adds twice to alkynes

18 Radical addition of H–Br to HBr, hγ anti-Markovnikov-selective; radical process 46 Alkyne double halogenation Cl2, Br2, or I2 Each individual reaction is anti-selective
alkenes (2 equiv)

19 Hydrogenation of alkenes Pd/C, H2 syn- selective 47 Halogenation Cl2, Br2, or I2 anti-selective

(1 equiv)

20 Alkene chlorination Cl2, CCl4 anti- selective 48 Addition of H–Cl to Alkynes H–Cl Markovnikov selective

21 Alkene bromination Br2, CCl4 anti- selective 49 Addition of H–Br to Alkynes H–Br Markovnikov selective

22 Alkene iodination I2, CCl4 anti- selective 50 Addition of H–I to Alkynes H–I Markovnikov selective

23 Chlorohydrin formation Cl2, H2O anti- selective; Markovnikov selective, water

is solvent. Alcohol solvent gives ether 51 Addition of H–X to H–Cl, H–Br, Markovnikov selective
or NCS haloalkenes or H–I
24 Bromohydrin formation Br2, H2O anti- selective; Markovnikov selective, water
is solvent. Alcohol solvent gives ether 52 Double addition of H–Cl to H–Cl [2 equiv] Adds twice to alkyne; Markovnikov selective
or NBS
anti- selective; Markovnikov selective, water Alkynes
25 Iodohydrin formation Cl2, H2O
is solvent. Alcohol solvent gives ether
or NIS 53 Double addition of H–Br to H–Br [2 equiv] Adds twice to alkyne; Markovnikov selective
26 Epoxidation of alkenes RCO3H anti- selective; Markovnikov selective, water Alkynes
is solvent. Alcohol solvent gives ether
(e.g. m-CPBA) H–I [2 equiv]
54 Double addition of H–I to Adds twice to alkyne; Markovnikov selective
27 Dihydroxylation of alkenes OsO4, KHSO3 syn- selective. KHSO3 helps remove Os
Alkynes
with OsO4
(e.g. m-CPBA)
55 Elimination of dihalides to NaNH2 [2 vicinal or geminal dihalides; for terminal
28 Dihydroxylation of alkenes KMnO4, NaOH syn- selective. Important to keep cold, equiv]
otherwise oxidative cleavage occurs (see 31) give alkynes alkynes, 3 equiv NaNH2 required
(cold KMnO4) (cold, dilute)