Electrophilic Addition Reactions of Alkenes & Oxidation and Cyclopropanation Reactions of Alkenes

1. H — X

X = Cl, Br, I

Markovnikov orientation

Rearrangement can occur

Hydrohalogenation

Hydrohalogenation

1. H — H (H₂)

metal

Metal = Pt or Pd or Ni

Syn stereochemistry

No rearrangement

Catalytic Hydrogenation

Catalytic Hydrogenation

1. X—X (X₂) & H₂O

X = Cl, Br

Markovnikov orientation

anti stereochemistry

No rearrangement

and enantiomer

Halohydrin Formation

Halohydrin Formation

1. X—X (X₂)

X = Cl, Br

anti stereochemistry

no rearrangement

and enantiomer

Halogenation

Halogenation

1. BH₃ / THF

2. H₂O₂ / NaOH

anti-Markovnikov orientation

syn stereochemistry

no rearrangement

and enantiomer

Hydroboration-oxidation

Hydroboration-oxidation

1. H—OR / Hg(OAc)₂

2. NaBH₄

Markovnikov orientation

no rearrangement

Alkoxymercuration-demurcuration

Alkoxymercuration-demurcuration

1. Hg(OAc)₂, H₂O

2. NaBH₄

Markovnikov orientation

no rearrangement

Oxymercuration-demercuration

Oxymercuration-demercuration

1. H₂O / H⁺ catalyst

Markovnikov orientation

rearrangement can occur

Hydration

Hydration

1. (in photo)

syn stereochemistry

no rearrangement

and enantiomer

Epoxidation

Epoxidation

1. CHBr₃ / KOH and H₂O

syn stereochemistry

no rearrangement

and enantiomer

Cyclopropanation by alpha elimination

Cyclopropanation by alpha elimination

1. CH₂I₂, Zn, CuCl

syn stereochemistry

no rearrangement

and enantiomer

Simmons-Smith

Simmons-Smith

1. O₃

2. (CH₃)₂S

produces ketones and aldehydes

Ozonolysis

Ozonolysis

1. KMnO₄, H₂O, heat

produces ketones and carboxylic acids

Oxidative Cleavage by KMnO₄

Oxidative Cleavage by KMnO₄

1. OsO₄ + H₂O₂ or KMnO₄ + HO^-

syn stereochemistry

no rearrangement

and enantiomer

Syn dihydroxylation

Syn dihydroxylation

1. H⁺ catalyst, H₂O, (look at picture)

from epoxide intermediate

anti stereochemistry

no rearrangement

and enantiomer

Anti dihydroxylation

Anti dihydroxylation