Organic Addition Reactions: Hydrohalogenation, Hydration, and More Save

Simple Protic solvents:

water, methanol, ethanol

Simple Polar Aprotic solvents:

DMSO, DMF, acetone

Simple Non-Polar solvents:

hexane, toluene

Simple Neutral/Mid Polar solvents:

ether, THF, DCM

Her, Hal or HI in a simple solvent

Hydrohalogenation Reagents

H₂O + acid (H₂SO₄, H₃O⁺)

Hydration Reagents

1) Hg(OAc)₂, H₂O (in THF) 2) NaBH₂

Oxymercuration-Demurcuration

Alcohol (ROH) + Hg (OAc)₂, then NaBH₄

Alkoxymercuration-Demercuration

BH₃ or 9-BBN, 2) H₂O₂, OH^-

Hydroboration-Oxidation

Br₂ or Cl₂ in an inert solvent (like CCl₄)

Halogenation

Br₂ (or Cl₂) in water

Halohydrin Formation

H₂ gas + metal catalyst (Pd, Pt, or Ni)

Hydrogenation

Preacid (e.g., mCPBA)

Epoxidation

OsO₄ (osmium tetroxide) then NaHSO₃ (or NMO) — syn addition.
Or KMnO₄ cold and dilute — syn addition but less selective.

Dihydroxylation (adding two OH’s)

O₃ then (CH₃)₂S (reductive workup) → gives aldehydes/ketones.
O₃ then H₂O₂ (oxidative workup) → aldehydes can be oxidized to acids.

Ozonolysis (cleavage of double bond)

Hot, concentrated KMnO₄

Oxidative Cleavage

Olefin Metathesis

Grubbs or Schrock catalysts (special metal complexes).

Olefin Metathesis

H to less substituted C, X/OH to more substituted (typical acid or H-X additions).

Markovinkov

Hydroboration-oxidation (OH to less substituted) or HBr with peroxides (Br to less substituted).

Anti-Markovnikov