Typical Notes [1°, 2° and 3° refers to

Reaction Name Conditions primary, secondary, tertiary]

Reaction Map: Reactions of Alkanes, Alkyl Halides, Alkenes, Alkynes and Alcohols 1
Free radical chlorination Cl2, hγ Not highly selective

2 Free radical bromination Br 2, hγ Highly selective for tertiary C–H

56

3 Elimination [E2] RO /ROH Best for 2° and 3°, anti stereochemistry

Geminal Vicinal Vicinal Diols 57

Alkenyl halides Dihalides Dihalides Halohydrins Elimination [E1] polar solvent, Competes with SN1
Cyclopropanes 4
X H X X X HO X HO OH heat
51 X
R H R R R R R Epoxides 5 Alcohol Formation [SN2] OH / H 2O Best for 1° alkyl halides; 2° can compete w/ E2
O
6 Alcohol Formation [SN1] H 2O Best for 3° alkyl halides; rearr possible w/ 2°
55 R "Solvolysis"
50 54 55 22 23 27
33 Ether Formation [SN2] Best for 1° alkyl halides; 2° can compete w/ E2
49 21 7 RO /ROH
24 32 26 ["Williamson Ether Synthesis"]
53 28
48 20 Ether Formation [SN1] ROH Best for 3° alkyl halides; rearr possible w/ 2°
25 69 8
52 "Solvolysis"

Ethers 9 Thiol formation [SN2] SH SN2; best for 1° alkyl halides, 2° OK

Alkenyl dihalides Alkynes Alkenes 35
34 R OR
47 39 40
R X R C C R
R 10 Sulfide formation [SN2] SR SN2; best for 1° alkyl halides, 2° OK
X R 59 8 Ring opened in
41 36 Ester formation [SN2] RCO 2 SN2; best for 1° alkyl halides, 2° OK
products 11 polar
46 29 37
47 58 7 60 HO aprotic
42 15 38 solvent
45 30 Azide formation [SN2] N3 SN2; best for 1° alkyl halides, 2° OK
19 R Nu 12
43 16 Alcohols
31
Tetrahalides Nitrile formation [SN2] CN SN2; best for 1° alkyl halides, 2° OK
R OH 13
X X 44 17
X X
R R Disulfides 14 Alkyne formation [SN2] R C C Best for 1° alkyl halides; 2° can compete w/ E2
18 61
R S S R
"Carbonyls"
15 Addition of H-Cl To Alkenes H–Cl Markovnikov-selective; rearr. possible
HO 68 67 66 62 8
O
O 6 65 16 Addition of H-Br To Alkenes H–Br Markovnikov-selective; rearr. possible
63 7
O 4
Alkanes
64 5 Thiols 17 Addition of H-I To Alkenes H–I Markovnikov-selective; rearr. possible
R–H 3
1 R SH
18 Radical addition of H–Br to HBr, hγ anti-Markovnikov-selective; radical process
2 alkenes
Alkyl Halides 9
10 Hydrogenation of alkenes Pd/C, H 2 syn- selective
R–X 19
14
Alkyl Sulfonates 20 Alkene chlorination Cl2, CCl4 anti- selective
10
This "map" includes reactions typically covered in chapters covering: R–OTs Sulfides
R–OMs ["Thioethers"]
21 Alkene bromination Br 2, CCl4 anti- selective
•Substitution and eliimination reactions of alkyl halides R SR
• Reactions of alkenes
• Reactions of alkynes 11
22 Alkene iodination I 2, CCl4 anti- selective
• Free-radical substitution of alkanes 13 12
• Alcohols and thiols
23 Chlorohydrin formation Cl2, H 2O anti- selective; Markovnikov selective, water
It will be expanded as subsequent chapters are covered or NCS is solvent. Alcohol solvent gives ether
Esters anti- selective; Markovnikov selective, water
24 Bromohydrin formation Br 2, H 2O
Please feel free to add comments or sugestions! O or NBS is solvent. Alcohol solvent gives ether
Nitriles Azides R O
R C N 25 Iodohydrin formation Cl2, H 2O anti- selective; Markovnikov selective, water
R N3 R is solvent. Alcohol solvent gives ether
or NIS
26 Epoxidation of alkenes RCO 3H anti- selective; Markovnikov selective, water
is solvent. Alcohol solvent gives ether
(e.g. m-CPBA)
27 Dihydroxylation of alkenes OsO 4, KHSO 3 syn- selective. KHSO 3 helps remove Os
with OsO 4 (e.g. m-CPBA)
28 Dihydroxylation of alkenes KMnO 4, NaOH syn- selective. Important to keep cold,
(cold KMnO 4) (cold, dilute) otherwise oxidative cleavage occurs (see 31)

29 Ozonolysis (reductive O 3, then Zn/H+ or cleaves C=C to give two carbonyls. Alkenyl
workup) (CH3)2S C-H bonds remain

30 Ozonolysis (oxidative O 3, then H 2O 2 cleaves C=C to give two carbonyls. Alkenyl

workup) C-H bonds oxidized to C–OH
31 Oxidative cleavage with KMnO 4, acid, cleaves C=C to give two carbonyls. Alkenyl 56 Formation of epoxides from NaH (strong Internal SN2 reaction: inversion of
KMnO 4 heat C-H bonds oxidized to C–OH halohydrins base) configuration at carbon

32 Cyclopropanation (Simmons- Cu/Zn, CH2I 2 syn-selective H 3O+ (or

57 Opening of epoxides with Protonation of epoxide, then attack of H 2O at
Smith)
aqueous acid H 2O/H 2SO4 ) most substituted carbon
33 Dichlorocyclopropanation CHCl3, KOH syn-selective
58 Elimination of alcohols to H 2SO4, heat Follows Zaitsev's rule (most sub. alkene
34 Acid-catalyzed ether H 2SO4, ROH Markovnikov selective, rearr. possible form alkenes (acidic) formed). Rearrangements can occur
formation POCl 3,
59 POCl 3 elimination of E2 reaction
35 Oxymercuration Hg(OAc) 2, ROH, Markovnikov selective, alcohol is solvent alcohols to alkenes pyridine
then NaBH 4
36 Oxymercuration Hg(OAc) 2, H 2O, Markovnikov selective, water is solvent 60 Acidic cleavage of ethers HI, heat Can proceed through SN2 or SN1 depending
then NaBH 4 on type of alcohol

37 Hydroboration BH 3, then NaOH, anti-Markovnikov selective, syn-selective 61 Conversion of alcohols to PBr 3 SN2 reaction. PCl 3 can also be used to make
H 2O 2 alkyl halides with PBr 3 alkyl chlorides
38 Acid-catalyzed hydration H 2SO4, H 2O Markovnikov selective; rearr possible
62 SOCl2 conversion of SOCl2 Usually taught as SN2. Pyridine can be used
("H3O+")
alcohols to alkyl chlorides as base.
39 Partial hydrogenation Lindlar, H 2 syn-selective
(Lindlar) 63 Alcohols to alkyl halides HCl, HBr, HI Can go through SN1 or SN2 depending on
with HX type of alcohol
40 Partial hydrogenation Na/NH 3 anti-selective
(sodium reduction)
64 Tosylate and mesylate TsCl or MsCl Does not affect stereochemistry. Can use a
41 Alkyne hydroboration BH 3, then NaOH, anti-Markovnikov selective; tautomerization formation base such as pyridine.
H 2O 2

42 Alkyne Oxymercuration HgSO 4, H 2O, Markovnikov selective; tautomerization 65 Disulfide formation I 2 (oxidant) Can use other oxidants but I 2 is most
H 2SO4 common

43 Alkyne Ozonolysis O3 Carboxylic acids formed; terminal alkynes 66 Alcohol oxidation with PCC PCC 1° alcohols to aldehydes; 2° alcohols to
give CO2 ketones

67 Alcohol oxidation with K 2Cr2O 7 + 1° alcohols to carboxylic acids, 2° alcohols

44 Alkyne Ox. Cleavage KMnO 4, H + same as ozonolysis to ketones.
H 2CrO4 acid
[KMnO 4]

45 Hydrogenation Pd/C, H 2 Adds twice to alkynes 68 Dess Martin oxidation Dess Martin 1° alcohols to aldehydes; 2° alcohols to
Periodinane ketones

46 Alkyne double halogenation Cl2, Br 2, or I 2 Each individual reaction is anti-selective 69 Basic ring opening of Grignards, Add to least substituted position of epoxides
(2 equiv) epoxides –OH, LiAlH
4

47 Halogenation Cl2, Br 2, or I 2 anti-selective

(1 equiv)

48 Addition of H–Cl to Alkynes H–Cl Markovnikov selective

49 Addition of H–Br to Alkynes H–Br Markovnikov selective

50 Addition of H–I to Alkynes H–I Markovnikov selective

51 Addition of H–X to H–Cl, H–Br, Markovnikov selective

haloalkenes or H–I

52 Double addition of H–Cl to H–Cl [2 equiv] Adds twice to alkyne; Markovnikov selective
Alkynes

53 Double addition of H–Br to H–Br [2 equiv] Adds twice to alkyne; Markovnikov selective
Alkynes

54 Double addition of H–I to H–I [2 equiv] Adds twice to alkyne; Markovnikov selective
Alkynes

55 Elimination of dihalides to NaNH 2 [2 vicinal or geminal dihalides; for terminal

give alkynes equiv] alkynes, 3 equiv NaNH 2 required