Reactions of Alkenes: Summary

Intermediate: Regiochemisty: Addition: Rearrangements? Carbocation Radical 3-Membered Ring None or Cyclic (concerted) Markovnikov-like Anti no N/A Syn no

Markovnikov* Anti-Markovnikov* Syn & Anti yes Syn & Anti 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

Alkyl halide
X H3C

Carbocation

syn + anti

Markovnikov

HBr, ROOR CH3 heat or light (NOT HCl or HI) Br CH3

Alkyl halide

Radical

syn + anti

Anti-Markovnikov

X2
CH3

Vicinal dihalide
X X
CH3

(X = Br, Cl)

3-membered ring

anti

Markovnikov-like

X2, H2O

(X = Br, Cl)
CH3

CH3 OH

Halohydrin

3-membered ring

anti

Markovnikov-like

H3O+, H2O
OH CH3

Alcohol

Carbocation

syn + anti

Markovnikov

H3C

1. Hg(OAc)2, H2O CH3 2. NaBH4

OH

Alcohol

3-membered ring

anti

Markovnikov-like

H3C

1. BH3, THF CH3 2. HOOH, NaOH HO CH3

Alcohol

None (concerted)

syn

Anti-Markovnikov

CH3

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

H3 C

OCH3

Ether

3-membered ring

anti

Markovnikov-like

CHX3, KOH CH3

X C X

CH3

Cyclopropane

None (concerted)

syn

N/A

CH2I2, Zn(Cu) CH3

H C

CH3
H

Cyclopropane

None (concerted)

syn

N/A

H2, Pd/C

CH3

(or H2, PtO2)

Alkane
CH3

Heterogeneous

syn

N/A

RCO3H CH3
O

CH3

Epoxide

None (concerted)

syn

N/A

H3O+, H2O

CH3

HO

OH CH3

trans-1,2-diol

3-membered ring

anti

N/A

OH, H2O HO CH3 OH

CH3

trans-1,2-diol

None (concerted)

anti

N/A

1. OsO4 CH3 2. NaHSO3, H2O (or H2O 2) HO CH3 OH

cis-1,2-diol

Cyclic (concerted)

syn

KMnO4 (cold, dilute)

-

CH3

OH, H2O

HO

CH3 OH

cis-1,2-diol

Cyclic (concerted)

syn

HO

CH3 OH

HIO4, H2O H O O CH3

Aldehydes and Ketones

Cyclic (concerted)

syn

1. O3 CH3 2. Zn(H3O ) or (CH3)2S

+

H O O

CH3

Aldehydes and Ketones

Cyclic (concerted)

syn

1. O3 CH3 2. H2O2

HO O O

CH3

Carboxylic acids and Ketones

Cyclic (concerted)

syn

KMnO4 (hot, conc'd) CH3 H3O+, H2O

HO O O

CH3

Carboxylic acids and Ketones

Cyclic (concerted)

syn