Mechanisms Flashcards
Reagents: HX
HydroHalide Addition to Pi Bond
- Markovnikov Regiochemistry
- Carbocation Rearrangement

Reagents: Weak Nucleophile, Strong Acid Catalyst (Typically H2O, H3O+)
Acid-Catalyzed Hydration of Pi Bond - Markovnikov Regiochemistry - Carbocation Rearrangement

Reagents: 1) Hg(OAc)2, HOH, THF
2) NaBH4
Oxymercuration / Demercuration
- Markovnikov Regiochemistry
- Anti/Trans Stereochemistry
- No Carbocation Rearrangement

Reagents: 1) Hg(OAc)2, HOR, THF
2) NaBH4
Alkoxymercuration / Demercuration
- Markovnikov Regiochemistry
- Anti/Trans Stereochemistry
- No Carbocation Rearrangement

Reagents: 1) BH3, THF
2) H2O2, NaOH, H2O
Hydroboration Oxidation
- Anti-Markovnikov Regiochemistry
- Syn / Cis Stereochemistry
- Carbocation Rearrangement

Reagents: HX, ROOR (peroxides), heat or light
Anti-Mark HydroHalide Addition to Pi Bond
- Anti-Markovnikov Regiochemistry
- Carbocation Rearrangement

Reagents: Br2 or Br2, HOR
Electrophilic Addition of Br2 to Pi Bond (Bromonium Ion)
- Markovnikov Regiochemistry
- Anti / Trans Stereochemistry
- No Carbocation Rearrangement

Reagents: Peroxy Acid (ROOOH) (Typically MCPBA)
Epoxide Ring Formation

Reagents: 1) MCPBA
2) H+, HOR
Epoxide Ring Opening (Acidic Conditions)
- Markovnikov Regiochemistry (follows the carbocation)
- Anti / Trans Stereochemistry
- No Carbocation Rearrangement
- Can Add 2 OH or 1 OH & 1 OR Group

Reagents: 1) MCPBA
2) Strong Base (HOR, NR2-, NaR)
3) Dilute Acid or RX
Epoxide Ring Opening (Basic Conditions)
- Anti-Markovnikov Regiochemistry (goes for spot with less steric hindrance)
- Anti / Trans Stereochemistry
- Can Add 2 OH, 2 OR, or 1 OH & 1 OR Group

Reagents: CHCl3, KOH or CH2I2, Zn(Cu)
Cyclopropane Ring from a Pi Bond
- Carbene addition to the pi bond
- Carbenes need to be made in situ

Reagents: H2, Pt or Pd metal
Strongly Catalyzed Reduction of Pi Bonds
- Syn / Cis Stereochemistry
- Reduces all Pi Bonds in Alkenes and Alkynes

Reagents: H2, Ni2B or H2, Lindlar Catalyst
Weakly Catalyzed Reduction of Pi bonds
- Syn / Cis Stereochemistry
- Only Reduces first Pi Bond in Alkenes and Alkynes

Reagents: Na metal, NH3 liquid
Weakly Catalyzed Reduction of Pi Bonds
- Anti / Trans Stereochemistry
- Only Reduces first Pi Bond in Alkenes and Alkynes

Reagents: PCC
Oxidation of Primary Alcohol to Aldehyde
- Removes two H’s to form double bond across C-O
- Weaker oxidizing agent

Reagents: KMnO4 or Na2Cr2O7, acid, water or CrO3, acid, water
Oxidation of Secondary Alcohol to Ketone or Oxidation of Aldehyde to Carboxylic Acid
- Removes two H’s to form double bond across C-O
- Oxidizes vinyl H’s on Aldehydes into OH’s
- Stronger oxidizing agents

Reagents: 1) OsO4
2) H2O2 or NaHSO3
Syn Addition of 2 OH’s to a Pi Bond
- Syn / Cis Stereochemistry
- No epoxide ring necessary to get similar product

Reagents: 1) O3 (ozone)
2) Zn, acetic acid
Ozonolysis
- Oxidative Cleavage of Sigma and Pi Bond
- “Cauterized” by oxygen molecule to create two new molecules
- Weak oxidizing agent, so vinyl H’s are untouched

Reagents: 1) hot KMnO4
2) H3O+, H2O
Permanganate
- Oxidative Cleavage of Sigma and Pi Bond
- “Cauterized” by oxygen molecule to create two new molecules
- Strong oxidizing agent, so vinyl H’s are oxidized into OH’s

Reagents: Excess HX
HX Addition to Alkynes
- Markovnikov Regiochemistry
- Creates Geminal Dihalide (adds on same C)

Reagents: Excess X2
X2 Addition to Alkynes
- Markovnikov Regiochemistry
- Anti / Trans Products
- Creates Geminal Tetrahalides (adds on same 2 C’s)

Reagents: H30+, Vinyl Alcohol (OH on a C=C)
Tautomerization
- The Enol form (vinyl alcohol) shifts to it’s more stable Keto form (ketone with C=O)
- Reversible
- Exception to stability is phenols (benzylic more stable than allylic)

Reagents: Catalytic Acid, H2O or H2SO4 or HgSO4 (+ Alkyne)
Acid-Catalyzed Hydration of Alkyne
- Markovnikov Regiochemistry
- Produces an Enol that tautomerizes into a Ketone

Reagents: 1) BH3, THF (+ Alkyne)
2) H202, NaOH, H2O
Hydroboration Oxidation of Alkyne
- Anti-Markovnikov Regiochemistry
- Syn / Cis Stereochemistry
- Produces an Enol that tautomerizes into a Ketone

Reagents: NaNH2
Produces Acetylide Anion
- Deprotonates an Alkyne to create a nucleophile

Reagents: H2O, H2SO4 (+ Nitrile)
Nitrile Hydrolysis
- Like other alkynes, this creates an Enol product that tautomerizes to a Ketone
