Ochem Chapter 8- alkene reactions

H-X

• HCl

• HBr

• HI

• etc

markovnikov

carbocation rearrangement

stereospecific!

• both TS are closer to the intermediate

H-X with radical RO-OR + heat

antimarkovnikov

rearrangement- radical stability

Acid Hydration 

H2O + H2SO4

Markovnikov

carbocation rearrangements

1) Hg(OAc)2, H2O 

2) NABH4

Oxymercuration- Demuercuration Hydration

Markovnikov

No rearrangments 

Anti addition of OH+H

1) Hg(OAc)2, CH3OH 

2) NABH4

Alkoxyl Mercuration

Markovnikov

No rearrangements

Anti addition of ROH

1) BH3, THF

2) H2O2, NaOH

Hydroboration Hydration

Antimarkovnikov

No rearrangements

Syn addition H+OH

X2

Inert solvent

Br2

Ch2Cl2

Anti addition of X2

X2

polar protic solvent 

Cl2

H2O 

Markovnikov 

anti addition of H+OH (halohydrin formation)

halohydrin: has both halogen and OH

H2

Catalysts: Pd, Pt, Ni

alien spaceship

syn addition of H+H

• doesn’t effect aromatic rings

CH2N2

heat

Diazomethane

syn addition of carbene

CH2I2

Zn(Cu)

Simmons Smith

syn addition of carbene

CHBr3, CHCl3

strong base 

alpha elimination

syn addition

O3- RCO3H or mPBA

CH2Cl2

syn addition of epoxides

acid catalyzed opening of epoxides

markovnikov

anti addition of OH+OH

OsO4/ H2O2

KMnO4/ OH

syn addition of OH+OH

KMnO4 + H3O

KMnO4 + (warm, concerted)

Oxidative cleavage

separate two and add =O

replace the cleaved part H with OH

• H3O acidic environment causes CO2 and H2O formation through keto enol

O3

(CH3)2S

Ozonolysis

Miilder; Produces Ketones and aldehydes

separate two and add =O, H doesn’t turn into OH