Hypervalent iodine

Dess-Martin periodane: Selective oxidation of prim. alcohols to aldehydes, sec. alcohols to ketones

- Rely on conversion of 1, 2 alcohol into activated ester followed by elimination! a. Dess-Martin: Periodinane
Preparation:
HO I
KBrO3/H2O

Non-metallic Reagents Dess-Martin Oxidation

O I O O
CH3COOH (CH3CO)2O 100 oC

CH3COO OCOCH3 I OCOCH3 O O

COOH

H2SO4

IBX: Iodoxybenzoic acid

Oxidation of I(1) to I(V), then esterification/ nucleophilic addition!

Example:
CH3COO OCOCH3 I OCOCH3

CH3CH2 CH3CH2

O O H3C

CH3

O O

CH3CH2 CH3CH2

O O H3C

CH3

OH

CH2Cl2, 25 oC

98%

Relies on oxidizing power of I(V). Very easy to carry out. By-product from oxidant is very easily removed and recycled!

Dess-Martin Oxidation - Mechanism

H CH3COO OCOCH3 I OCOCH3 O O :O H H R' R H + R CH3COO O R I OCOCH3 O -OCOCH 3 O CH3COO O H R R I OCOCH3 O H OCOCH O

Alcohol is activated by attachment of redox active leaving group by SN reaction on I(V)! Activated alcohol has O H R' H3C been detected. H OCOCH3 R OCOCH3 Reduction of I(V) to I(III). O O + I I OCOCH3 Decomposition pathway of R' O + O ester to ketone unknown.
O O O R

OCOCH3

O I O + OH
i. KBrO3/H2O/H2SO4 ii. CH3COOH/(CH3CO)2O 100 oC

Reduction product is recycled!

I O O

H2 O

CH3COO OCOCH3 I OCOCH3 O O

H OCOCH3

Periodic acid
Diol cleavage

Oxidation of Glycols
Glycols are cleaved by oxidation with periodic acid, HIO4.
OH + OH cis- 1,2-Cyclohexanediol HIO 4 Periodic acid CHO CHO Hexanedial

+ HIO 3 Iodic acid

Oxidation of Glycols
The mechanism of periodic acid oxidation of a glycol is divided into two steps. Step 1: Formation of a cyclic periodate.
C OH + O C OH O I O OH C O O C O I OH + H2 O

O A cyclic period ate

Step 2: Redistribution of electrons within the ring.

O C C O I O O OH C O O C O O I

OH

Oxidation of Glycols
This mechanism is consistent with the fact that HIO4 oxidations are restricted to glycols that can form a five-membered cyclic periodate. Glycols that cannot form a cyclic periodate are not oxidized by HIO4.
OH HO OH The t rans is omer is un reactive tow ard periodic acid Th e cis is omer forms a cyclic periodate and is cleaved OH HIO4 O O

Recall Periodic Acid Oxidation

Section 15.12: Vicinal diols are cleaved by HIO4. HIO4 OH

C HO

O + O

Cleavage of a vicinal diol consumes 1 mol of HIO4.

Also Cleaved by HIO4

a-Hydroxy carbonyl compounds O RC C OH HIO4 HO R C O + O C

Cleavage of an a-hydroxy carbonyl compound consumes 1 mol of HIO4. One of the products is a carboxylic acid.

Also Cleaved by HIO4

Compounds that contain three contiguous carbons bearing OH groups O CH CR'2 HIO4 R2C O + HCOH OH OH

R2C HO

+ R'2C

2 mol of HIO4 are consumed. 1 mole of formic acid is produced.

Distinguish between furanose and pyranose forms of methyl arabinoside HOCH2 O OH OH O

Structure Determination Using HIO4

HO

HO

OCH3

HO

OCH3

2 vicinal OH groups; consumes 1 mol of HIO4

3 vicinal OH groups; consumes 2 mol of HIO4