Selenoxide Elimination

SELENOXIDE ELIMINATION
• Selenoxide elimination is a method for the chemical

synthesis of alkenes from selenoxides.
• It is used to synthesize α,β-unsaturated carbonyl compounds.
 Elimination of selenoxides takes

place through an intramolecular syn
elimination pathway.
 The carbon–hydrogen and carbon–
selenium bonds are co-planar in the
transition state
1
Department of Chemistry (UIS) www.cuchd.in
DEHYDRATION OF ALCOHOLS
 The dehydration of alcohols to form symmetrical ethers
• The dehydration of alcohols is an

elimination reaction that takes place
under acidic rather than basic
conditions and involves an E1
mechanism
 The elimination
step is expected to
favor the more-
substituted alkene
Carey and Sundberg, Advanced Organic Chemistry, Part A: Structure and Mechanisms, 5th Edition, 2007
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COREY–WINTER REACTION
 Cyclic thionocarbonates can be cleaved to alkenes by heating with
trimethyl phosphite or other trivalent phosphorus compounds or
by treatment with bis(1,5 cyclooctadiene)nickel complex.
 The elimination is of course syn, so the product is sterically
controlled
• Preparation of thionocarbonates
Smith and Jerry March, Advanced Organic Chemistry, Sixth Edition, 2007
4
Conversion of 1,2-diols to alkenes. The cyclic thiocarbonate is available from reaction of the
diol with thiophosgene or thiocarbonyldiimidazole, and reacts with
added trimethylphosphite via a syn-elimination to the alkene.
Mechanism of the Corey-Winter Olefin Synthesis
It is assumed that the reaction proceeds with attack of phosphite on sulphur leading to
a carbene, which may react with a second equivalent of phosphite during the
cycloreversion that splits out carbon dioxide and yields the product alkene.
REDUCTION OF ALKYNES
Clayden, J., Greeves, N. and Warren, S., “Organic Chemistry”, Oxford University Press,2012
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OLEFIN METATHESIS
• Carbenes can be stabilized as transition metal

complexes
• These carbene-derived complexes are important
because of a remarkable reaction known as
alkene/olefin metathesis.
Clayden, J., Greeves, N. and Warren, S., “Organic Chemistry”, Oxford University Press,2012
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OLEFIN METATHESIS
• When a simple diene reacts with Grubb’s catalyst,
cyclization reaction occurs to give an alkene.
• Two carbon atoms are lost as ethylene.
• An exchange of groups between the two arms of the
molecule takes place.
Department of Chemistry (UIS)

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MECHANISM
 First, the carbene complex adds to one of the alkenes
in what can be drawn as a [2 + 2] cycloaddition.
 Reverse reaction happens to give a new carbene

complex and styrene.
Clayden, J., Greeves, N. and Warren, S., “Organic Chemistry”,

Department Oxford(UIS)
of Chemistry
University Press,2012 www.cuchd.in
10
CONTINUED
 Next, an intramolecular [2 + 2] cycloaddition joins up
the five-membered ring and produces a second
metalla cyclobutane, which decomposes in the same
way as the first one to give a third carbene complex
and the product.
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This new carbene complex is then ready to attack
another molecule of starting material and the cycle is
repeated, with the minor difference that ethylene
(ethene) is now lost instead of styrene in the first step.
RING-CLOSING METATHESIS
• The Grubbs catalyst is compatible with forming cyclic
alkenes by ring-closing metathesis.
• Intramolecular reactions generate rings, usually
alkenes or dienes.
Example:

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ENYNE METATHESIS
 Enyne metathesis is the reaction of an olefin and
an alkyne to produce a 1,3-diene.
 Metathesis with vinyl-cyclopropyl-alkynes is also
known, producing a ring expanded product.
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THE THORPE REACTION
 In the Thorpe reaction, the α-carbon of one nitrile
molecule is added to the CN carbon of another.
 This reaction is analogous to the aldol reaction.
• The C=NH bond is hydrolyzable, so β-keto nitriles can

be prepared

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Thorpe–Ziegler reaction: is the intramolecular modification with a dinitrile
as a reactant and a cyclic ketone as the final reaction product after acidic
hydrolysis. The reaction is conceptually related to the Dieckmann
condensation.
Thorpe–Ziegler
reaction
COREY–FUCHS REACTION
 The Corey–Fuchs reaction, also known as
the Ramirez–Corey–Fuchs reaction, is a series
of chemical reactions designed to transform
an aldehyde into an alkyne.
Department of Chemistry (UIS) 20

MECHANISM
Step
1
Step2
Step
3
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SEYFERTH-GILBERT HOMOLOGATION
 The Seyferth–Gilbert homologation is a chemical

reaction of an aryl ketone (or aldehyde) with dimethyl
(diazomethyl)phosphonate and potassium tert-
butoxide to give substituted alkynes.
• Dimethyl (diazomethyl)phosphonate is often called

the Seyferth Gilbert reagent.
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MECHANISM
 This reaction is called a homologation because the
product has exactly one additional carbon more than the
starting material.
Seyferth–Gilbert reagent A
Oxaphosphetane D
Dimethylphosphate E
Vinyldiazo-intermediate Fa and Fb
Vinyl carbene G
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OHIRA-BESTMANN MODIFICATION
• Dimethyl (diazomethyl)phosphonate can be
generated in situ from dimethyl-1-diazo-2-
oxopropylphosphonate (also called the Ohira-
Bestmann reagent) by reaction
with methanol and potassium carbonate.
in situ generation of the Ohira-Bestmann reagent
https://en.wikipedia.org/wiki/Seyferth%E2%80%93Gil
Department
bert_homologationof Chemistry (UIS) www.cuchd.in
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SELENOXIDE ELIMINATION

• Selenoxide elimination is a method for the chemical

 Elimination of selenoxides takes

• The dehydration of alcohols is an

• Carbenes can be stabilized as transition metal

Department of Chemistry (UIS)

 Reverse reaction happens to give a new carbene

Clayden, J., Greeves, N. and Warren, S., “Organic Chemistry”,

Department of Chemistry (UIS) www.cuchd.in

• The C=NH bond is hydrolyzable, so β-keto nitriles can

Department of Chemistry (UIS)

Department of Chemistry (UIS) 20

 The Seyferth–Gilbert homologation is a chemical

• Dimethyl (diazomethyl)phosphonate is often called

in situ generation of the Ohira-Bestmann reagent

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