Reactions of Alkenes: Summary

Intermediate:

Carbocation

Regiochemisty:

Markovnikov* Anti-Markovnikov*

Addition:
Rearrangements?

Radical

3-Membered Ring None or Cyclic (concerted)

Markovnikov-like

N/A

Syn & Anti

Syn & Anti

Anti

Syn

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

(X = Br, Cl, I)
CH3

heat or light
(NOT HCl or HI)

Br

(X = Br, Cl)

(X = Br, Cl)
CH3

CH3
OH

H3O+, H2O
OH
CH3

Alkyl halide

Radical

syn + anti

Anti-Markovnikov

Vicinal dihalide

3-membered
ring

anti

Markovnikov-like

Halohydrin

3-membered
ring

anti

Markovnikov-like

Alcohol

Carbocation

syn + anti

Markovnikov

Alcohol

3-membered
ring

anti

Markovnikov-like

Alcohol

None
(concerted)

syn

Anti-Markovnikov

H3C

1. Hg(OAc)2, H2O
2. NaBH4

OH

H3C

1. BH3, THF
CH3

Markovnikov

CH3

X2, H2O

CH3

syn + anti

CH3

X2
CH3

Carbocation

H3C

HBr, ROOR
CH3

Alkyl halide
X

2. HOOH, NaOH

HO

CH3

CH3

1. Hg(OAc )2, MeOH

2. NaBH4

H3 C

CHX3, KOH
CH3

OCH3

Ether

3-membered
ring

anti

CH3

Cyclopropane

None
(concerted)

syn

N/A

Cyclopropane

None
(concerted)

syn

N/A

Alkane

Heterogeneous

syn

N/A

Epoxide

None
(concerted)

syn

N/A

trans-1,2-diol

3-membered
ring

anti

N/A

trans-1,2-diol

None
(concerted)

anti

N/A

CH2I2, Zn(Cu)
CH3

CH3
H

H2, Pd/C

CH3

(or H2, PtO2)

CH3

RCO3H
CH3

CH3

H3O+, H2O

CH3

HO

OH
CH3

OH, H2O

CH3

Markovnikov-like

HO

CH3
OH

Cyclic
(concerted)

syn

Cyclic
(concerted)

syn

Cyclic
(concerted)

syn

Aldehydes
and Ketones

Cyclic
(concerted)

syn

CH3

Carboxylic acids
and Ketones

Cyclic
(concerted)

syn

CH3

Carboxylic acids and

Ketones

Cyclic
(concerted)

syn

1. OsO4
CH3

2. NaHSO3, H2O

(or H2O 2)

HO

CH3
OH

HO

CH3
OH

KMnO4 (cold, dilute)

-

OH, H2O

CH3

HO

CH3
OH

HIO4, H2O
H

CH3

cis-1,2-diol

cis-1,2-diol

Aldehydes
and Ketones

O O

1. O3
CH3

2. Zn(H3O ) or (CH3)2S

1. O3
CH3

H3O+, H2O

CH3
O O

HO

2. H2O2

KMnO4 (hot, conc'd)

CH3

O O

HO
O O