Addition Reactions of Alkenes

Reactants, Catalyst, Markovnikov, Rearrangements, Stereochemistry

Hydrogenation

H₂, metal catalyst (Ni, Pd, Pt, Rh), syn-addition

Oxymercuration Demercuration

Hg(OAc)₂, Markovnikov, no rearr., no stereochem

Hydroboration Oxidation

BH₃, peroxide, Anti-Markovnikov, no rearr. SYN-addition

Ionic Addition *know mechanism!

HBr, HI, no catalyst, Markovnikov, yes rearr (carbocation)

reaction: SN1 or E1 - can either attack carbocation directly or attack hydrogens adjacent

Radical Addition

Ionic (HBr, HI) but with peroxide (ROOR) on bottom, but Non-Markovnikov (H on higher degree, Br on lower) - do not need to know mechanism

Halogenation

Br₂, Cl₂, Markovnikov, no rearr. ANTI-ADDITION

Halohydrogenation

Halogenation alt, Br₂ and H2O - second Br becomes OH (markovnikov - on higher degree)

Simmons-Smith Cyclopropane

CH2 (Carbene) or CH₂I₂ / Zn(Cu)

replace alkene w party hat

Syn-Dihydroxylation

Syn additions, no rearr.

TWO ALCS on double bond:

• Os, pyridine, H₂O = two alcs

• KMnO₄, cold, H₂O = 2 alcs

Oxidative Cleavage

OH product if:

• KMnO₄, Heat

H product if:

• O₃ (ozone)

If any carbon is terminally double bonded (CH₂), CO₂ will be generated as a product.