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Chapter 7

The Reactions
of Alkynes
An Introduction to
Multistep Synthesis

Paula Yurkanis Bruice


University of California,
Santa Barbara
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Nomenclature of Alkynes
An alkyne is a hydrocarbon that contains a carboncarbon triple bond.
General formula: CnH2n2 (acyclic)
CnH2n4 (cyclic)

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Nomenclature of Alkynes

The yne suffix is assigned the lowest number.


The substituents are assigned so the lowest number is in the name.

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Two of the Same Functional Group

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A Double Bond and a Triple Bond

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Double and Triple are Tied

When the same number is obtained for both,


the double bond gets the lower number.

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Priority of Functional Groups Suffixes

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OH and NH2 Have Higher Priority

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Physical Properties of Unsaturated


Hydrocarbons

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The Structure of Alkynes

The triple bond is composed of a sigma bond and two bonds.


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Alkynes (Like Alkenes) Undergo


Electrophilic Addition Reactions

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Alkynes Are Less Stable and


Less Reactive Than Alkenes

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The First Step is Addition of an Electrophile

Addition of an electrophile
to an alkene

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Addition of an electrophile
to an alkyne

Relative Carbocation Stability

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Formation of a -Complex
A primary vinylic cation is less sable than a primary alkyl cation.

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Evidence for Formation of a -Complex

Evidence for the formation of a -complex

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A Second Addition Reaction Can Occur

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Addition to a Terminal Alkyne is


Regioselective

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Mechanism for Electrophilic Addition

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Formation of the More Stable Transition State


Accounts for the Regioselectivity

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The Second Electrophilic Addition Reaction is


Also Regioselective

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Formation of the More Stable Carbocation


Accounts for the Regioselectivity

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The Second Electrophilic Addition


Reaction is Slower

This explains why if only one equivalent of HCl is used,


the reaction stops at the halo-substituted alkene.

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An Asymmetrical Internal Alkyne


Forms Two Products

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A Symmetrical Internal Alkyne


Forms One Product

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Addition of Cl2 and Br2

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Acid-Catalyzed Addition of
Water to an Alkene

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Acid-Catalyzed Addition of
Water to an Alkene

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KetoEnol Interconversion

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Mechanism for Acid-Catalyzed


KetoEnol Interconversion

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Acid-Catalyzed Addition of Water

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A Terminal Alkyne is Less Reactive


Than an Internal Alkyne

Because terminal alkynes are less reactive, the rate of the


reaction is increased with a mercuric ion catalyst.

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Mechanism for Catalysis by Hg2+

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HydroborationOxidation

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BH3 Is an Electrophile

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9-BBN or R2BH

R2BH should be used with terminal alkynes.

R2BH can be used with internal alkynes.


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HydroborationOxidation

Terminal alkynes form aldehydes.


Internal alkynes form ketones.
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Addition of Hydrogen Forms an Alkane

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Stopping at the Alkene

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Lindlar Catalyst

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Syn Addition

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Why Cis?

The catalyst delivers the hydrogens to one side of the triple bond.
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Anti Addition

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Mechanism for Formation of a


Trans Alkene

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Why Trans?

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Relative Electronegativities of Carbon

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A Hydrogen Attached to an sp Carbon


is the Most Acidic

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Need a Strong Base to Remove


the Hydrogen

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HO is Not Strong Enough

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Relative Acid Strengths

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Forming a New CarbonCarbon Bond

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Mechanism for Formation of the


CarbonCarbon Bond

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Two Steps

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How Can the Compound Be Prepared


From the Starting Material?

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Synthesis

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Retrosynthetic Analysis and Synthesis

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Designing a Synthesis

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Retrosynthetic Analysis and Synthesis

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Designing a Synthesis

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Retrosynthetic Analysis and Synthesis

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Designing a Synthesis

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Retrosynthetic Analysis and Synthesis

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Designing a Synthesis

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Retrosynthetic Analysis and Synthesis

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Designing a Synthesis

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Retrosynthetic Analysis and Synthesis

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Designing a Synthesis

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Retrosynthetic Analysis and Synthesis

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Designing a Synthesis

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Retrosynthetic Analysis and Synthesis

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