Addition Reactions

Addition Reactions of Alkenes and Alkynes

Hydrohalogenation of Alkene Transformation

Alkene to alkyl halide

Hydrohalogenation of Alkene (non ROOR) Regiochemistry and Stereochemistry

R: Markovnikov

S: Racemic

Hydrohalogenation of Alkene (ROOR) Regiochemistry and Stereochemistry

R: Anti-Markovnikov

S: Racemic

Hydrohalogenation of Alkene Reactants

Alkene + HBr in CCl₄ or H₂O₂

Acid-Catalyzed Hydration of Alkene Transformation

Alkene to alcohol

Acid-Catalyzed Hydration of Alkene Regiochemistry and Stereochemistry 

R: Markovnikov (possible rearrangement)

S: Racemic 

Acid-Catalyzed Hydration of Alkene Reactants 

Alkene + acid + H₂O or ROH

Oxymercuration-Demercuration of Alkene Transformation

Alkene to alcohol 

Oxymercuration-Demercuration of Alkene Regiochemistry and Stereochemistry 

R: Markovnikov 

S: Racemic 

Oxymercuration-Demercuration of Alkene Reactants

Step 1: Alkene + Hg(OAc)₂ + nucleophile, H₂O, or ROH

Step 2: Mercurinium ion + NaBH₄

Hydroboration-Oxidation of Alkene Transformation

Alkene to alcohol

Hydroboration-Oxidation of Alkene Regiochemistry and Stereochemistry

R: Anti-Markovnikov

S: Syn addition

Hydroboration-Oxidation of Alkene Reactants

Step 1: Alkene + BH₃ in THF

Step 2: H₂O₂ + NaOH

Catalytic Hydrogenation of Alkene Transformation

Alkene to Alkane

Catalytic Hydrogenation of Alkene Regiochemistry and Stereochemistry

R: Both sides add H

S: Racemic syn addition

Catalytic Hydrogenation of Alkene Reactants

Alkene + H₂ + metal (Pt or Pd)

Halogenation of Alkene Transformation

Alkene to alkyl dihalide

Halogenation of Alkene Regiochemistry and Stereochemistry

R: Vinyl

S: Syn for trans, anti for cis 

Halogenation of Alkene Reactants

Alkene + Br₂ or Cl₂

Halohydrin Formation of Alkene Transformation

Alkene to alkyl halide with an alcohol

Halohydrin Formation of Alkene Regiochemistry and Stereochemistry

R: Alcohol Markovnikov, halide anti-Markovnikov

S: Anti

Halohydrin Formation of Alkene Reactants

Alkene + Br₂ + xs H₂O or other nucleophile

Anti Dihydroxylation of Alkene Transformation

Alkene to alkane with two alcohol groups

Anti Dihydroxylation of Alkene Regiochemistry and Stereochemistry

R: OH adds to both sides of pi bond

S: Anti

Anti Dihydroxylation of Alkene Reactants

Step 1: Alkene + RCO₃H (peroxyacid) or peroxyacetic acid or MCPBA and H

Step 2: H₃O⁺ or other acid

Syn Dihydroxylation of Alkene Transformation

Alkene to alkane with two alcohol groups

Syn Dihydroxylation of Alkene Regiochemistry and Stereochemistry

R: OH adds to both sides

S: Syn

Syn Dihydroxylation of Alkene Reactants

Step 1: Alkene + OsO₄

Step 2: H₂O + NaHSO₃ or NMO

Oxidative Cleavage of Alkene Transformation

Alkene to mix of ketone and aldehyde (alkene can be cyclic)

Oxidative Cleavage of Alkene Regiochemistry and Stereochemistry

R: N/A
S: N/A

Oxidative Cleavage of Alkene Reactants

Step 1: Alkene + O₃

Step 2: DMS or Zn/H₂O

Catalytic Hydrogenation of Alkyne Transformation

Alkyne to alkane

Catalytic Hydrogenation of Alkyne Regiochemistry and Stereochemistry

R: N/A

S: N/A

Catalytic Hydrogenation of Alkyne Reactants

Step 1&2: Alkyne + xs H₂ + Pt or Pd

Poisoned Catalytic Hydrogenation of Alkyne Transformation

Alkyne to cis alkene

Poisoned Catalytic Hydrogenation of Alkyne Regiochemistry and Stereochemistry

R: N/A

S: Syn

Poisoned Catalytic Hydrogenation of Alkyne Reactants

Alkyne + 1 eq. H₂ + poisoned catalyst (lindler’s catalyst or Ni₂B)

Dissolving Metal Reduction of Internal Alkyne Transformation

Alkyne to trans alkene

Dissolving Metal Reduction of Internal Alkyne Regiochemistry and Stereochemistry

R: N/A

S: Anti

Dissolving Metal Reduction of Internal Alkyne Reactants

Na in cold NH₃

Hydrohalogenation of Alkyne Transformation

Alkyne to alkyl halide on alkene

Hydrohalogenation of Alkyne Regiochemistry and Stereochemistry

R: Markovnikov

S: Racemic

Hydrohalogenation of Alkyne Reactants

Alkyne + 1 eq HX

Dihalide Hydrohalogenation of Alkyne Transformation

Alkyne to geminal dihalide on alkane

Dihalide Hydrohalogenation of Alkyne Regiochemistry and Stereochemistry

R: Markovnikov

S: Racemic

Dihalide Hydrohalogenation of Alkyne Reactants

Alkyne + xs HX

Interconversion of Dihalides to Alkynes Transformation

Dihalide to alkyne

Interconversion of Dihalides to Alkynes Regiochemistry and Stereochemistry

R: N/A

S: N/A

Interconversion of Dihalides to Alkynes Reactants

Step 1: Dihalide + xs NaNH₂ in NH₃

Step 2: H₂O

Radical Addition of HBr to Alkyne Transformation

Alyne to alkyl halide on alkene

Radical Addition of HBr to Alkyne Regiochemistry and Stereochemistry

R: Anti-Markovnikov

S: Racemic

Radical Addition of HBr to Alkyne Reactants

Alkyne + HBr + ROOR (H₂O₂)

Acid-Catalyzed Hydration of Alkyne Transformation

Alkyne to ketone

Acid-Catalyzed Hydration of Alkyne Regiochemistry and Stereochemistry

R: Markovnikov

S: N/A

Acid-Catalyzed Hydration of Alkyne Reactants

Alkyne + H₂SO₄ + H₂O in HgSO₄

Hydroboration-Oxidation of Alkyne Transformation

Terminal alkyne to aldehyde

Hydroboration-Oxidation of Alkyne Regiochemistry and Stereochemistry

R: Anti-Markovnikov

S: N/A

Hydroboration-Oxidation of Alkyne Reactants

Step 1: Alkyne + 9-BBN or disamylborane

Step 2: H₂O₂ + NaOH

Tetrahalide Halogenation of Alkyne Transformation

Alkyne to tetrahalide on alkane

Tetrahalide Halogenation of Alkyne Regiochemistry and Stereochemistry

R: X adds to both sides of pi bond

S: N/A

Tetrahalide Halogenation of Alkyne Reactants

Alkyne + xs X₂ in CCl₄

Dihalide Halogenation of Alkyne Transformation

Alkyne to major trans dihalide on alkene and minor cis dihalide on alkene

Dihalide Halogenation of Alkyne Regiochemistry and Stereochemistry

R: X adds to both sides of the pi bond

S: Anti major and syn minor

Dihalide Halogenation of Alkyne Reactants

Alkyne + 1 eq. X₂ in CCl₄

Ozonolysis of Alkyne Transformation

Internal alkyne to two carboxylic acids and terminal alkyne to a carboxylic acid and CO₂

Ozonolysis of Alkyne Regiochemistry and Stereochemistry

R: Internal is not selective, terminal C-C becomes carboxylic acid and C-H becomes CO₂

S: N/A

Ozonolysis of Alkyne Reactants

Step 1: Alkyne + O₃

Step 2: H₂O

Alkylation of Terminal Alkene Transformation

Terminal alkyne to a longer alkyne

Alkylation of Terminal Alkene Regiochemistry and Stereochemistry

R: Must be side of C-H bond

S: N/A

Alkylation of Terminal Alkene Reactants

Step 1: NaNH₂

Step 2: RX (R is methyl or ethyl)