Oxidation Methods

C543 Oxidation

3 main types of oxidation reagents

• Activated DMSO

• Chromium-based

• Hypervalent Iodine

What is the main reagent used in the Pfitzner-Moffatt oxidation?

Activated DMSO

What oxidation mechanism is shown?

Pfitzner-Moffatt

What main reagent is used in the Parikh-Doering reaction?

Activated DMSO

What mechanism is being shown?

Parikh-Doering

What is the main reagent used in the Swern oxidation?

Activated DMSO

What mechanism is being shown?

Swern

What is the main reagent in the Corey-Kim oxidation?

Activated DMS

What mechanism is being shown?

Corey-Kim

What is oxidized in the Pfitzner-Moffatt oxidation?

• Primary alcohols —> aldehydes

• Secondary alcohols —> ketones

What is oxidized in the Parikh-Doering oxidation?

• Primary alcohols —> aldehydes

• Secondary alcohols —> ketones

What is oxidized in the Swern oxidation?

• Primary alcohols —> aldehydes

• Secondary alcohols —> ketones

What is oxidized in the Corey-Kim oxidation?

• Primary alcohols —> aldehydes

• Secondary alcohols —> ketones

What is the main reagent used in the Jones oxidation?

Chromic (VI) acid

What is oxidized in the Jones oxidation?

• Secondary alcohols —> ketones

• Primary alcohols —> carboxylic acids

What mechanism is being shown?

Jones oxidation

What is the main reagent used in the Sarrett and Collins oxidations?

Dipyridine Chromium(VI) Oxide (CrO3-pyr2)

What is oxidized in Sarrett and Collins oxidations?

• Primary alcohols —> aldehydes

• Secondary alcohols —> ketones

What mechanism is shown?

Sarrett and Collins oxidation

What is the main reagent in the Corey-Suggs oxidation?

Pyridinium Chlorochromate (VI) (PCC)

What is oxidized in the Corey-Suggs oxidation?

• Primary alcohols —> aldehydes

• Secondary alcohols —> ketones

What mechanism is being shown?

Corey-Suggs

What is the main reagent used in the Cornforth oxidation?

Pyridinium Dichromate (VI) (PDC)

What is oxidized in the Cornforth oxidation?

• Primary alcohols —> aldehydes (DCM) or carboxylic acids (DMF)

• Secondary alcohols —> ketones

What mechanism is being shown?

Cornforth oxidation

What is the main reagent used in the Dess-Martin oxidation?

Dess-Martin Periodinane (DMP)

What is oxidized in the Dess-Martin oxidation?

• Primary alcohols —> aldehydes

• Secondary alcohols —> ketones

What mechanism is being shown?

Dess-Martinn periodiane oxidation

What mechanism is being shown?

IBX oxidation

What is the main reagent used in an IBX oxidation?

2-iodoxybenzoic acid (V) (IBX)

What is oxidized in an IBX oxidation?

• Primary alcohols —> aldehydes

• Secondary alcohols —> ketones

What does Manganese Dioxide oxidize?

• Allylic, Benzylic and Propargylic alcohols —> aldehydes and ketones

What does the Ley-Griffith reaction oxidize?

• Allylic and benzylic alcohols (rapid, unless sterically encumbered)

• Primary alcohols —> aldehydes

• Secondary alcohols —> ketones

What is the main reagent used in the Ley-Griffith oxidation?

Tetra-n-PropylAmmonium Perruthenate (TPAP)

What does 2,2,6,6-tetramethylpiperidine N-oxyl radical (TEMPO) oxidize?

• Primary alcohols —> aldehydes

• Secondary alcohols —> ketones

What is the main reagent used in the Oppenauer oxidation?

Aluminum Triisopropoxide

What is oxidized in the Oppenauer reaction?

• Primary alcohols —> aldehydes

• Secondary alcohols —> ketones

What is the main reagent used in the Pinnick oxidation?

Sodium chlorite (NaClO2)

What is oxidized in the Pinnick reaction?

• Aldehydes —> carboxylic acids

What is the main reagent used in the Baeyer-Villiger reaction?

m-CPBA

What is oxidized in the Baeyer-Villiger reaction?

• Ketones —> esters and carboxylic acids

What is the main reagent used in a Rubottom oxidation?

LDA then m-CPBA

What is oxidized in the Rubottom reaction?

• Enol ethers —> alpha hydroxyketone

What is the main reagent used in a Saegusa-Ito oxidation?

Pd(OAc)2

What is oxidized in a Saegusa-Ito reaction?

• Carbonyl compounds —> α,β-unsaturated ketones

What is the main reagent used in a Selenoxide elimination?

LDA, then PhSeBr

What is oxidized in a Selenoxide elimination?

• Carbonyl —> alpha-beta unsaturation (alkene formation)

What is the main reagent used in the Prilezhaev reaction?

m-CPBA

What happens in the Prilezhaev reaction?

• Electron rich alkenes —> epoxide (more sterically accessible = fastest)

What is the main reagent used in a basic peroxide reaction?

NaOH, H2O2, NeOH or DCM

What happens in a basic peroxide reaction?

• Electron deficient alkenes —> epoxide (i.e next to a carbonyl)

What is the main reagent used in alcohol directed basic peroxide reaction?

VO(acac)2

What happens in an alcohol directed basic peroxide reaction?

• Alkenes with an allylic alcohol —> epoxide

What is the main reagent used in a Shi epoxidation?

DMDO (acetone + oxone)

What happens in a Shi epoxidation?

• Alkenes —> epoxide (enantioselective)

What is the main reagent used in the Upjohn procedure?

Osmium tetroxide (OsO4)

What happens in the Upjohn reaction?

• Alkene —> dihydroxylation (enantioselective based on alpha/bottom or beta/top attack)

What is the main reagent used in the Riley oxidation?

SeO2

What happens in the Riley oxidation?

• Terminal double bond —> alcohol

• Alkene alpha to a carbonyl (due to rearrangement) —> carbonyl

• Ring —> alcohol (alpha to the more substituted side of the alkene)