Lecture 32

November 19th, 2014

Chapter 7
Alkynes

Reactions Learned
Have Learned
Last Time
1. Acidity of terminal alkynes - formation of terminal alkyne aions
[(CH3)2CH]2N-Li+

Na+HSodium hydride

Lithium diisopropylamide
(LDA)

N- Li+

2. Alkylation of alkyn anions with methyl or 1o halide

Alkylation side reaction

with 2 or 3o halide

Br
H C C

Na+

+
H

elimination
(Chapter 9)

H C C H +

Na+Br-

3. Synthesis of an alkyne from an alkene.

Br

Mechanism

CH3
Br

H3C
H
H
(Meso)

Na+NH2-

haloalkene
CH3 CH3
H
Na+NH2-

alkyne
H3CC CCH3

Br

Reactions to Learn Today

Alkyne reactions today:

Alkyne reactions next time:

Addition of X2 - halogenation

Hydroboration-Protonolysis to syn-alkene

Addition of HX - hydrohalogenation

Reducing with Lindlar Catalyst to

syn-alkene

Hydroboration - oxidation (hydration)

Reducing using Na or Li to
trans-Alkene
Acid - catalyzed hydration

Catalytic reduction to alkane

3

Addition of X2
Alkynes add one mole of bromine to give a
dibromoalkene. Addition shows anti
stereoselectivity.

Addition of second mole of bromine gives a

tetrabromoalkane.

Addition of X2
Addition of bromine to an alkyne follows much the same
mechanism as that for the bromination of an alkene,
namely formation of a bridged bromonium ion
intermediate, which is then attacked by bromide ion from
the face opposite that occupied by the positively charged
bromine atom. Addition of second mole of bromine gives
a tetrabromoalkane.
1st mole
of Br2:

2nd mole
of Br2:
5

Addition of HX
Alkynes undergo regioselective addition of either
1 or 2 moles of HX, depending on the ratios in
which the alkyne and halogen acid are mixed.
Addition of both the first and secod moles of HX is
regioselective, follows Markovnikovs rule.

Addition of HX
1st mole of HX
Step 1: Make a new bond between a nucleophile (a !
bond) and an electrophile - add a proton.
Nucleophile

Electrophile

Alkynes are considerable less reactive towards most electrophilic

additions than alkenes are. The major reason for this difference is
the instability of the sp-hybridized vinylic carbocation
intermediate formed from an akyne compared with the sp2hybridized alkyl carbocation formed from an alkene.

Step 2: Make a new bond between a nucleophile and

an electrophile.
Electrophile

Nucleophile

Addition of HX
2nd mole of HX
In the addition of the second mole of HX, step 1 is
reaction of the electron pair of the remaining !
bond with HBr to form a carbocation.
Of the two possible carbocations, the resonancestabilized 2 carbocation is favored.

Question
Problem
Whats the reaction product?
Et

Et

HCl (1.0 eqiv.)

Cl

HCl (1.0 eqiv.)

Et
Cl
Cl

Hydroboration
Addition of borane to an alkyne is called
hydrboration, and gives a trialkenylborane.
Addition is syn stereoselective.
Syn addition

10

Hydroboration
Mechanism:
Step 1:
Coordination of the vacant
2p orbital of boron with the
electron pair of the ! bond.
"#

"+

Step 2:
After coordination, the boron (electrophile) adds
to the less substituted carbon of the alkyne !
bond (nucleophile), thereby placing the hydrogen
on the more substituted carbon.
"# "+

more substituted C

syn-addition

nonMarkovnikov

cyclic fourcentered TS

Terminal alkynes react regioselectively with

borane, and H adds to the more substituted
carbon as non-Markovnikovs rule.
11

Hydroboration
"# "+

"#

more substituted C

"+

nonMarkovnikov

We account for the regioselectivity by:

1. Steric factor: Boron, the larger part of the reagent, adds
to the less hindered carbon; Hydrogen adds to the more
substituted carbon.
2. Electronic factor: Boron bearing a partial positive
charge and hydrogen a partial negative charge. It believed
there is some degree of carbon carbcation character in the
transition state and that the partial positive charge is on
the more substituted carbon.
12

Hydroboration
Hydroboration-Oxidation

The hydroboration reaction is difficult to stop

at this stage because the alkenyl group reacts
further with borane to undergo a second
hydroboration.
2nd
R
R

Hydroboration
R

Terminal alkyne
nonMarkovnikov

nonMarkovnikov

13

Hydroboration
To prevent dihydroboration with terminal alkynes, it is
necessary to use a sterically hindered dialkylborane,
such as (sia)2BH.

Treatment of a terminal alkyne with (sia)2BH results in

stereoselective and regioselective mono-hydroboration.

14

Hydroboration-Oxidation
to
Aldehyde
Hydroboration-Oxidation
and Ketone

Trialkylboranes are rarely isolated. They are

converted directly to other products formed by
substitution of another atom for boron. One
important reaction is treating an alkenylborane with
H2O2 in aqueous NaOH gives an enol. The net
reaction from hydroboration and subsequent
oxidation of alkyne is a hydration of the carboncarbon triple bond.
2. H2O2, NaOH

1. BH3
H

trialkenylborane

hydration
H

OH

2-buten-2-ol
( a enol)

Enol: A compound containing an -OH group on one

carbon of a carbon-carbon double bond.
15

Hydroboration-Oxidation to Aldehyde
and Ketone
An enol is in equilibrium with a keto form by migration
of a hydrogen from oxygen to carbon and migration of
the double bond from C=C to C=O.
Keto forms generally predominate at equilibrium.
Keto and enol forms are tautomers and their
interconversion is called tautomerism.
tautomerism
tautomerization
Keq = 6.7 x 106

1. BH3
2. H2O2, NaOH H

tautomerism mechanism

OH

2-buten-2-ol
( a enol)

H
O

2-butanone
(a ketone)
H

H
H

O H

O H

( a enol)
OH

O
O

H
O

(a ketone)

16

Hydroboration-Oxidation to Aldehyde
and Ketone
Hydroboration/oxidation of an internal alkyne gives a
ketone.
H

HO

1.BH3

2. H2O2, NaOH
3-Hexyne

An enol

3-Hexanone

Hydroboration/oxidation of a terminal alkyne gives an

aldehyde. Formation of enol follows non-Markovnicovs
rule, and hydrogen adds to the more substituted carbon.
1. (sia)2BH
2. H2O2, NaOH
1-Octyne

O
OH

H
An enol

non-Markovnicov

H
Octanal

17

Addition of H2O: hydration

In the presence of concentrated sulfuric acid and
Hg(II) salts, alkynes undergo addition of
water.Hydrogen adds to the less substituted
carbon following Markovnikovs rule.
Hydration

Markovnicov

18

Question
Problem
Whats the reaction product?

1)
H

Li
(1.0 equiv.)

H
2)

Br

3) H2O, Hg(OAc)2

OH

19

Reduction to Alkane

Treatment of an alkyne with H2 in the presence of

a transition metal catalyst, most commonly Pd,
Pt, or Ni, converts the alkyne to an alkane.

20

Reduction to Alkane
Mechanism:
Step 1: The metal adsorbs hydrogen and the ! system of the
alkyne. One carbon adds a hydrogen and is released from the metal
surface. The second carbon then adds a hydrogen and is released from
the metal surface to form alkene intermediate.

21

Reduction to Alkane
Step 2: Repeat step 1 one more time. The metal adsorbs hydrogen
and the ! system of the intermediate alkene. One carbon adds a
hydrogen and is released from the metal surface. The second carbon
then adds a hydrogen and is released from the metal surface to form
alkane product.

22

Reactions to
Learned
Learn today
Alkyne reactions today:

Alkyne reactions next time:

1. Addition of X2 - halogenation

Hydroboration-Protonolysis to syn-alkene

2. Addition of HX - hydrohalogenation

Reducing with Lindlar Catalyst to

syn-alkene

Markovnikovs rule
3. Hydroboration - oxidation (hydration)
Reducing using Na or Li to
trans-Alkene
Non-Markovnikovs rule
4. Acid - catalyzed hydration
Markovnikovs rule
5. Catalytic reduction to alkane
23