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Chapter 20

Organic Chemistry
6th Edition
Paula Yurkanis Bruice

More About
OxidationReduction
Reactions

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Oxidation is always coupled with reduction.

Loss of electrons is oxidation.

Gain of electrons is reduction.

The oxidation state of a carbon atom equals the total


number of its CO, CN, and CX bonds.
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Reduction at carbon increases the number of CH bonds or


decreases the number of CO, CN, or CX bonds.
Oxidation at carbon decreases the number of CH bonds or
increases the number of CO, CN, or CX bonds.

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Hydrogen, sodium borohydride, and hydrazine are the


reducing agents:

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Bromine and chromic acid are the oxidizing agents:

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H2 as a Reducing Agent

H2, Pd on charcoal

Na or Li metal in
liq NH3

NaBH4 or LiAlH4

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Reduction by Catalytic Hydrogenation


Addition of two hydrogen atoms:

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Only the alkene substituted to benzene is reduced:

Reduction of carbonnitrogen double and triple bonds:

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Reduction of Ketones and Aldehydes

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Rosenmund Reduction

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Dissolving-Metal Reduction
Addition of an electron, a proton, an electron, and a proton:

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Reduction by Addition of
a Hydride Ion and a Proton

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Aldehydes, ketones, and acyl halides can be reduced to


alcohols by sodium borohydrides:

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LiAlH4 is a stronger reducing agent than NaBH4


LiAlH4 is used to reduce compounds that are
unreactive toward NaBH4

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DIBALH allows the addition of one equivalent of hydride


to an ester:

Replacing some of the hydrogens of LiAlH4 with OR


groups decreases the reactivity of the metal hydride:

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Formation of Amines by Reduction

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NaBH4 can be used to selectively reduce an aldehyde or


a keto group in a compound:

Alkenes and alkynes do not possess a partial positive


charge:

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Sodium borohydride can be used as a chemoselective


reducing agent:

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Oxidation of Alcohols

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Oxidation of a Primary Alcohol

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Mechanism of Alcohol Oxidation


by the Swern Oxidation

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Oxidation of Aldehydes and Ketones

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The Tollens reagent oxidizes only aldehydes:

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Both aldehydes and ketones can be oxidized by


peroxyacid: the BaeyerVilliger oxidation

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Mechanism of the
BaeyerVilliger Oxidation

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Predicting BaeyerVilliger reaction products:

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Controlling Stereochemistry
in Synthesis
An enantioselective reaction forms more of one
enantiomer than of another:

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Hydroxylation of Alkenes

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Mechanism for cis-Glycol Formation

Higher yields of the diol are obtained with osmium


tetroxide than with permaganate

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Oxidative Cleavage of 1,2-Diols

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Summary of Alkene Hydroxylation Reactions

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Permaganate Cleavage of Alkenes

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Examples of permaganate-mediated alkene cleavage


reactions:

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Oxidative Cleavage of Alkenes by


Ozonolysis

Examples:

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Structure of Ozone

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The alkene and ozone undergo a concerted six-electron


cycloaddition
Mechanism of ozonide formation:

The molozonide is unstable because it has two OO


bonds, but the ozonide is stable
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Ozonides can be cleaved to carbonyl compounds:

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Ozonolysis Mechanism

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Examples of the Oxidative Cleavage of


Alkenes by Ozonolysis

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The benzene ring is not oxidized under mild ozonolysis


conditions:

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Oxidative Cleavage of Alkynes


The same reagents that oxidize alkenes also oxidize
alkynes:

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Designing a Synthesis by Functional


Group Interconversion
Conversion of an aldehyde to other functional groups:

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Conversion of a Ketone into


an Ester or an Alcohol

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