Lecture 33

November 21st, 2014

CHAPTER 7
ALKYNES

Reactions to Learn
Announcement

Suggested questions from Brown:

Chapter 6: 6.17; 6.21; 6.28; 6.31; 6.35; 6.37; 6.40; 6.42;
6.45; 6.46; 6.48
Chapter 7: 7.8; 7.10; 7.11; 7.14; 7.20; 7.21; 7.25
Lecture on Monday, No Lecture on Wednesday
No discussion next week, normal office hour on
Tuesday 4:30-5:30

Reactions Learned
to Learn today
Alkyne reactions last time:

Alkyne reactions today:

1. Addition of X2 - halogenation

5. Catalytic reduction to alkane

2. Addition of HX - hydrohalogenation

Reducing with Lindlar Catalyst to

syn-alkene

Markovnikovs rule
3. Hydroboration - oxidation (hydration)

Hydroboration-Protonolysis to syn-alkene

Non-Markovnikovs rule
4. Acid - catalyzed hydration

Markovnikovs rule

Reducing using Na or Li to trans-Alkene

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. The
reduction occurs in to stages: (1) addition of 1
mole of H2 to form an alkene and (2) addition of
the second mole H2 to the alkene to form the
alkane.

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.

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.

Reduction to syn-Alkene: Lindlar Cat.

In most cases, it is not possible to stop the
reaction at the alkene stage.However, with the
Lindlar catalyst, the reduction stops at synstereoselective addition of one mole of H2 to
afford cis-alkene product.

syn-addition

It is thought that the role of lead (Pb) is to reduce

the amount of H2 absorbed, while quinoline
helps avoid the formation of unwanted byproducts,
but its hard to be more specific than that.
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Reduction
to syn-Alkene:
Hydroboration
- Protonolysis
Hydroboration-Protonolysis
Syn-stereoselective hydroboration gives a
syn-addition
trialkenylborane.

Treatment of a trialkenylborane with acetic acid

results in stereoselective replacement of B by H. The
net effect of hydroboration followed by protonolysis is
reduction of the alkyne to a cis-alkene. Thus this a
alternative method for Lindar reduction to provide a
cis-alkene.
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Reduction
trans-Alkene:
Dissolving to
Metal
Reduction
Dissolving Metal Reduction
Reduction of an alkyne with Na or Li in liquid
ammonia converts an alkyne to tans-alkene with
anti stereoselectivity.
anti-addition

Reduction to trans-Alkene:
Dissolving Metal Reduction
Step 1: A one-electron reduction. Addition of one
electron to the triple bond gives a radical anion, a
species containing negative charge and unpaired electron.
Na

Na+ + e-

e-

Step 2: Add a proton. The alkenyl radical anion (a very

strong base) abstracts a proton from solvent ammonia
(a very weak acid) and yields a radical.

The net effect of step 1 and 2 is to add one hydrogen

atom to the triple bond.

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Reduction to trans-Alkene:
Dissolving Metal Reduction
Step 3: A second one-electron reduction gives an
alkenyl anion.
This step establishes the configuration of the alkene
A trans alkenyl anion is more stable than its cis isomer.
e Step 4: Add a proton. A second acid-base reaction
gives the trans alkene.

The net effect of step 3 and 4 is to add the second

hydrogen atom to the triple bond.

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Question
Problem
Provide the reaction reagents in the box
based on the structure of the products.
Na or Li,
NH3 (liquid)
Lindlar Catalyst

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Organic Synthesis

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Organic Synthesis
Synthesis is generally the most important objective
of organic chemists, applicable to the preparation of
compounds for use as pharmaceuticals, plastics,
agrochemicals, and textile fibers.
A successful synthesis must
provide the desired product in maximum yield.
have the maximum control of stereochemistry and
regiochemistry.
do minimum damage to the environment (it must be a
green synthesis).
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Organic Synthesis
We analyze a target molecule in the following ways:
The carbon skeleton: Count the carbons in the target
molecule versus the available starting material so that you
know what fragment must be added or subtracted. how
can we put it together?
Our only method to date for forming a new C-C bond is the alkylation
of alkyne anions with 1 haloalkanes.

The functional groups: what are they, how can they be

used to facilitate formation of the carbon-skeleton of the
target molecule, and how can they be changed to give the
functional groups of the target molecule? Regiospecificity and sterospecificity need to be considered.
Work backward: Our strategy will be to work backwards
from the target molecule.

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Organic Synthesis
We use a method called a retrosynthesis and an
open arrow to symbolize a step in a retrosynthesis.
Retrosynthesis: A process of reasoning backwards
from a target molecule to a set of suitable starting
materials.
target
molecule

starting
materials

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Example - Palytoxin Retrosynthesis

The toxicity of palytoxin is due to its
binding to sodium pump of body

next page

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Example - Palytoxin Retrosynthesis

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Organic Synthesis
Target molecule: 2-heptanone

OH

OH

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Organic Synthesis
Starting materials are acetylene and 1-bromopentane.

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Question Question
Provide the reaction reagents or the missing starting
material in the box based on the structure of the
products.
1)NaNH2 (or other
strong base)
2)
I

reduction of alkyne
to trans alkene

Na or Li,
NH3 (liquid)

alkylation of terminal
alkyne to internal alkyne

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