9.

Alkynes: An
Introduction to Organic
Synthesis

Based on McMurry’s Organic Chemistry, 7th edition

◼ We will use alkyne chemistry to begin looking at general strategies

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 9.1 Naming Alkynes
◼ General hydrocarbon rules apply with “-yne” as a suffix indicating an
alkyne
◼ Numbering of chain with triple bond is set so that the smallest
number possible for the first carbon of the triple bond

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 9.2 Preparation of Alkynes: Elimination
Reactions of Dihalides
◼ Treatment of a 1,2-dihalidoalkane with KOH or NaOH produces a
two-fold elimination of HX
◼ Vicinal dihalides are available from addition of bromine or chlorine to
an alkene
◼ Intermediate is a vinyl halide

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 9.3 Reactions of Alkynes: Addition
of HX and X2
◼ Addition reactions of alkynes are similar to those of alkenes
◼ Intermediate alkene reacts further with excess reagent
◼ Regiospecificity according to Markovnikov

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 Electronic Structure of Alkynes
◼ Carbon-carbon triple bond results from sp orbital on each C forming
a sigma bond and unhybridized pX and py orbitals forming π bonds.
◼ The remaining sp orbitals form bonds to other atoms at 180º to C-C
triple bond.
◼ The bond is shorter and stronger than single or double
◼ Breaking a π bond in acetylene (HCCH) requires 318 kJ/mole (in
ethylene it is 268 kJ/mole)

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 Addition of Bromine and
Chlorine
◼ Initial addition gives trans intermediate
◼ Product with excess reagent is tetrahalide

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 Addition of HX to Alkynes Involves
Vinylic Carbocations
◼ Vinylic carbocation intermediate
◼ sp-hybridized: forms less readily than alkyl carbocation
◼ 2o vinyl carbocations ≈ 1o alkyl carbocations
◼ 1o vinyl carbocations probably do not form at all

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 Addition of HX to Alkynes Involves
Vinylic Carbocations
◼ Problem 9.3
◼ Expect the products

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 9.4 Hydration of Alkynes
◼ Addition of H-OH as in alkenes
◼ Mercury (II) catalyzes Markovinikov oriented addition
◼ Hydroboration-oxidation gives the non-Markovnikov product

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 Mercury(II)-Catalyzed Hydration of
Alkynes
◼ Alkynes do not react with aqueous protic acids
◼ Mercuric ion (as the sulfate) is a Lewis acid catalyst that promotes
addition of water in Markovnikov orientation
◼ The immediate product is a vinylic alcohol, or enol, which
spontaneously transforms to a ketone

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 Mechanism of Mercury(II)-
Catalyzed Hydration of Alkynes
◼ Addition of Hg(II) to alkyne gives a vinylic cation
◼ Water adds and loses a proton
◼ A proton from aqueous acid replaces Hg(II)

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 Keto-enol Tautomerism
◼ Isomeric compounds that can rapidily interconvert by the movement
of a proton are called tautomers and the phenomenon is called
tautomerism
◼ Enols rearrange to the isomeric ketone by the rapid transfer of a
proton from the hydroxyl to the alkene carbon
◼ The keto form is usually so stable compared to the enol that only the
keto form can be observed

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 Hydration of Unsymmetrical
Alkynes
◼ If the alkyl groups at either end of the C-C triple bond are not the
same, both products can form and this is not normally useful
◼ If the triple bond is at the first carbon of the chain (then H is what is
attached to one side) this is called a terminal alkyne
◼ Hydration of a terminal always gives the methyl ketone, which is
useful

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 Mercury(II)-Catalyzed Hydration of
Alkynes
◼ Problem 9.4
◼ Expect product

◼ Problem 9.5
◼ Starting alkyne?

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 Hydroboration/Oxidation of Alkynes
◼ BH3 (borane) adds to alkynes to give a vinylic borane
◼ Oxidation with H2O2 produces an enol that converts to the ketone or
aldehyde
◼ Process converts alkyne to ketone or aldehyde with orientation
opposite to mercuric ion catalyzed hydration

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 Comparison of Hydration of
Terminal Alkynes
◼ Hydroboration/oxidation converts terminal alkynes to aldehydes
because addition of water is non-Markovnikov
◼ The product from the mercury(II) catalyzed hydration converts
terminal alkynes to methyl ketones

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 Hydroboration/Oxidation of Alkynes
◼ Problem 9.6
◼ Starting alkyne (Use hydroboration/oxidation)?

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 9.5 Reduction of Alkynes
◼ Addition of H2 over a metal catalyst (such as palladium on carbon,
Pd/C) converts alkynes to alkanes (complete reduction)
◼ The addition of the first equivalent of H2 produces an alkene, which
is more reactive than the alkyne so the alkene is not observed

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Conversion of Alkynes to cis-Alkenes
◼ Addition of H2 using chemically deactivated palladium on calcium
carbonate as a catalyst (the Lindlar catalyst) produces a cis alkene
◼ The two hydrogens add syn (from the same side of the triple bond)

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Conversion of Alkynes to trans-Alkenes
◼ Dissolving metal reduction
◼ Anhydrous ammonia (NH3) is a liquid below -33 ºC
◼Alkali metals dissolve in liquid ammonia and function as
reducing agents
◼ Alkynes are reduced to trans alkenes with sodium or lithium in liquid
ammonia
◼ The reaction involves a radical anion intermediate

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9.6 Oxidative Cleavage of Alkynes
◼ Strong oxidizing reagents (O3 or KMnO4) cleave internal alkynes,
producing two carboxylic acids
◼ Terminal alkynes are oxidized to a carboxylic acid and carbon dioxide
◼ Neither process is useful in modern synthesis – were used to
elucidate structures because the products indicate the structure of the
alkyne precursor

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 9.7 Alkyne Acidity: Formation of
Acetylide Anions
◼ Terminal alkynes are weak Brønsted acids (alkenes and alkanes
are much less acidic (pKa ~ 25)
◼ Reaction of strong anhydrous bases with a terminal acetylene
produces an acetylide ion

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 9.7 Alkyne Acidity: Formation of
Acetylide Anions
◼ The sp-hydbridization at carbon holds negative charge relatively
close to the positive nucleus

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 9.8 Alkylation of Acetylide Anions
◼ Acetylide ions can react as nucleophiles as well as bases

◼ Reaction with a primary alkyl halide produces a hydrocarbon that

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 9.8 Alkylation of Acetylide Anions
◼ Mechanism (SN2 reaction…. !?)

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 Limitations of Alkyation of Acetylide
Ions
◼ Reactions only are efficient with 1º alkyl bromides and alkyl iodides
◼ Acetylide anions can behave as bases as well as nucelophiles
◼Nucleophile = Base !!!
◼ Reactions with 2º and 3º alkyl halides gives dehydrohalogenation,
converting alkyl halide to alkene

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 Alkyation of Acetylide Anions
◼ Problem 9.10
◼ Terminal alkyne & alkyl halide ?

◼ Problem 9.11
◼ Prepare cis-but-2-ene from propyne, alkyl halide, … (multiple
steps)

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 9.9 An Introduction to Organic
Synthesis
◼ Organic synthesis creates molecules by design
◼ Synthesis can produce new molecules that are needed as drugs or
materials
◼ Syntheses can be designed and tested to improve efficiency and
safety for making known molecules
◼ Highly advanced synthesis is used to test ideas and methods,
answering challenges
◼ Chemists who engage in synthesis may see some work as elegant
or beautiful when it uses novel ideas or combinations of steps – this
is very subjective and not part of an introductory course

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 Synthesis as a Tool for Learning
Organic Chemistry
◼ In order to propose a synthesis you must be familiar with reactions
◼ What they begin with
◼ What they lead to
◼ How they are accomplished
◼ What the limitations are
◼ A synthesis combines a series of proposed steps to go from a
defined set of reactants to a specified product
◼ Questions related to synthesis can include partial information
about a reaction of series that the student completes

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 Strategies for Synthesis
◼ Compare the target and the starting material
◼ Consider reactions that efficiently produce the outcome. Look at the
product and think of what can lead to it
◼ Worked Ex. 8.1
◼ Prepare octane from 1-pentyne

Retrosynthetic Analysis

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 Strategies for Synthesis
◼ Worked Ex. 9.2

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 Strategies for Synthesis
◼ Worked Ex. 9.3

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 Strategies for Synthesis
◼ Worked Ex. 9.4

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