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CHAPTER 7
ALKYNES
Reactions to Learn
Announcement
Reactions Learned
to Learn today
Alkyne reactions last time:
1. Addition of X2 - halogenation
2. Addition of HX - hydrohalogenation
Markovnikovs rule
3. Hydroboration - oxidation (hydration)
Hydroboration-Protonolysis to syn-alkene
Non-Markovnikovs rule
4. Acid - catalyzed hydration
Markovnikovs rule
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.
syn-addition
Reduction
to syn-Alkene:
Hydroboration
- Protonolysis
Hydroboration-Protonolysis
Syn-stereoselective hydroboration gives a
syn-addition
trialkenylborane.
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-
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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.
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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.
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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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next page
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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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