Reactions of Alkenes: Summary

Intermediate: Carbocation Radical 3-Membered Ring None or Cyclic (concerted)

Regiochemisty: Markovnikov* Anti-Markovnikov* Markovnikov-like N/A
Addition: Syn & Anti Syn & Anti Anti Syn
Rearrangements? yes no no no

*the reaction goes through the pathway of the most stable intermediate;
the more substituents on an electron deficient carbon (carbocation or radical), the greater its stability

Stereochemistry:
• If the reactants are optically inactive (achiral), the products will be optically inactive (achiral, racemic or meso)
• If the reactants are optically active (chiral), the products will be optically active (unequal mixture of
enantiomers, unequal mixture of diastereomers, or 1 enantiomer)
• Use 2n of the product to predict the maximum number of stereoisomers
(if just anti or just syn addition, divide the maximum number of stereoisomers by 2)

Predicting the type of intermediate:

• Carbocation - H is the electrophile (no lone pair to share with the empty p orbital)
• Radical - an initiator with a weak bond (ex. ROOR) and an energy source (heat or light) is present
• 3-Membered Ring - the electrophile has a lone pair of electrons available to share with the empty p orbital
• None or Cyclic - the electrophile can both accept and donate electrons at the same time
 HX
Alkyl halide Carbocation syn + anti Markovnikov
(X = Br, Cl, I) X
CH3 H3C

HBr, ROOR
Alkyl halide Radical syn + anti Anti-Markovnikov
heat or light
CH3 Br CH3
(NOT HCl or HI)

X2 Vicinal dihalide 3-membered anti Markovnikov-like

(X = Br, Cl) CH3 ring
CH3 X X

X2, H2O 3-membered

Halohydrin ring
anti Markovnikov-like
(X = Br, Cl) CH3
X OH
CH3

H3O+, H2O
Alcohol Carbocation syn + anti Markovnikov
OH
CH3 H3C

1. Hg(OAc)2, H2O
3-membered
OH Alcohol ring anti Markovnikov-like
2. NaBH4 H3C
CH3

1. BH3, THF None

Alcohol syn Anti-Markovnikov
CH3
2. HOOH, NaOH
HO CH3 (concerted)
 1. Hg(OAc )2, MeOH 3-membered
OCH3 Ether anti Markovnikov-like
2. NaBH4
H3 C
ring
CH3

CHX3, KOH None

CH3 Cyclopropane syn N/A
C (concerted)
CH3 X X

CH2I2, Zn(Cu) None

CH3
Cyclopropane (concerted) syn N/A
CH3 C
H H

H2, Pd/C
Alkane Heterogeneous syn N/A
(or H2, PtO2)
CH3 CH3

RCO3H
None
Epoxide (concerted) syn N/A
CH3 CH3
O

H3O+, H2O
trans-1,2-diol 3-membered anti N/A
O
CH3
HO
OH ring
CH3

-
OH, H2O None anti
trans-1,2-diol N/A
O
CH3 HO
CH3 (concerted)
OH
 1. OsO4 Cyclic
cis-1,2-diol syn
CH3
2. NaHSO3, H2O
CH3 (concerted)
(or H2O 2) HO OH

KMnO4 (cold, dilute) Cyclic

cis-1,2-diol syn
-
OH, H2O HO
CH3 (concerted)
CH3 OH

Cyclic
HIO4, H2O Aldehydes syn
CH3 (concerted)
HO OH H CH3 and Ketones
O O

1. O3
Aldehydes Cyclic
+ H CH3 (concerted) syn
CH3
2. Zn(H3O ) or (CH3)2S
O O
and Ketones

1. O3 Carboxylic acids Cyclic

HO CH3

(concerted) syn
2. H2O2
O O
and Ketones
CH3

KMnO4 (hot, conc'd) Carboxylic acids and Cyclic

HO CH3
Ketones (concerted) syn
CH3 H3O+, H2O O O