L8 Oxidation of Alcohols and Carbonyls

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11 Terms

1
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Basic mechanism for oxidation of an alcohol

Reduction of E

<p>Reduction of E</p>
2
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oxidation using Cr(VI) - CrO3

are more or less hindered alcohols oxidised faster

The slow rds has a greater release of steric strain as the transition from sp3 to sp2 occurs

An aldehyde forms an equilibrium with a hydrate which can then be oxidised further to a carboxylic acid (possibly unwanted)

<p>The slow rds has a greater release of steric strain as the transition from sp3 to sp2 occurs</p><p>An aldehyde forms an equilibrium with a hydrate which can then be oxidised further to a carboxylic acid (possibly unwanted)</p>
3
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Cr(VI) oxidants

Jones reagent needs acetone to dissolve.

PCC and PDC stop at aldehydes (/ketones)

Cr residues are very toxic however

<p>Jones reagent needs acetone to dissolve.</p><p>PCC and PDC stop at aldehydes (/ketones)</p><p>Cr residues are very toxic however</p>
4
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Catalytic alcohol oxidation using TPAP

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5
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TPAP mechanism for oxidation of alcohols

May need to use a desiccant to remove the water to prevent further oxidation.

The crucial step in the catalytic part is losing a lone pair of electrons on Ru

<p>May need to use a desiccant to remove the water to prevent further oxidation.</p><p>The crucial step in the catalytic part is losing a lone pair of electrons on Ru</p>
6
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Activated DMSO oxidations

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7
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Swern oxidation using DMSO

Activated using a di acyl chloride.

Quite mild and preserves the stereochemistry next to the aldehyde formed

<p>Activated using a di acyl chloride. </p><p>Quite mild and preserves the stereochemistry next to the aldehyde formed</p>
8
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Dess-Martin Periodinane

Follows the same mechanism formula as usual

<p>Follows the same mechanism formula as usual</p>
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Selective oxidation of allylic and benzylic alcohols

Using MnO2 a radical is formed and the reaction only proceeds with allylic or benzylic stabilisation next to the OH, hence the other alcohols are untouched.

<p>Using MnO<sub>2</sub> a radical is formed and the reaction only proceeds with allylic or benzylic stabilisation next to the OH, hence the other alcohols are untouched.</p>
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Pinnick oxidation of aldehydes to carboxylic acids

The alkene is there to remove the HOCl - the resulitng compound is quite volatile and can be removed easily e.g. via evaporation.

<p>The alkene is there to remove the HOCl - the resulitng compound is quite volatile and can be removed easily e.g. via evaporation.</p>
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Baeyer-Villiger reaction - cleavage of ketones to form esters.

If R is H, it migrates and a carboxylic acid is produced - less useful as the side product is also a carboxylic acid so separation is harder.

<p>If R is H, it migrates and a carboxylic acid is produced - less useful as the side product is also a carboxylic acid so separation is harder.</p>