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Mislow-Evans Rearrangement

Mislow-Evans rearrangement   Named Reactions in Organic Synthesis

Reaction category:
Pericyclic and photochemical reactions

Other featured pericyclic reactions:
Featured photochemical reactions:

In 1968 the German-born American chemist Kurt Mislow reported that when heating enantiomerically pure allylic sulfoxides they underwent thermal racemization whilst enantiopure allylic sulfenates gave optically active sulfoxides. In 1971 David Evans and colleagues realized the synthetic potential of this technique in converting allylic sulfoxides to allylic alcohols via a sulfonate ester intermediate in the presence of a thiophile, usually a phosphite or other nucleotide. They also showed that it was applicable for a wide range of substrates. The first step of this transformation is a [2,3-]-sigmatropic rearrangement of an allylic sulfoxide to a sulfenate ester which became known as the Mislow-Evans rearrangement.

The second phase of the Evans reaction is the alkylation of the allylic alcohol via formation of an intermediate carbanion. Typically the formation of the allylic carbanion is achieved through the use of a strong base such as n-butyl lithium or lithium diisopropylamide (LDA) at low temperatures. Alkylation of the allylic carbanion is also carried out at low temperatures in the presence of a variety of alkyl, allylic and benzylic halides.

The reaction has general application in the preparation of trans-allylic alcohols and the total synthesis of the major urinary metabolite of the hormone Prostaglandin E2 by Douglas Taber and colleagues utilized this to ensure the (E) stereochemistry of the double bond.

 

Mechanism of the Mislov-Evans reaction:

Mislov-Evans reaction mechanism


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Other reaction categories:

Electrophilic aromatic substitution

Nucleophilic substitution reactions

Heterocycle-formation

Transition metal-catalyzed couplings

Oxidation

Reactions involving carbonyl compounds

Reduction reactions

Rearrangement reactions

Electrophilic addition reactions


Some relevant Alfa Aesar products for the Mislow-Evans rearrangement:

n-Butyllithium, 2.2M in hexane, packaged under Argon in resealable ChemSeal™ bottles
n-Butyllithium, 2.2M in hexane
n-Butyllithium, 1.6M in hexanes, packaged under Argon in resealable ChemSeal™ bottles
n-Butyllithium, 2.5M in hexanes, packaged in resealable septum cap bottle
n-Butyllithium, 1.6M in hexane, packaged in resealable septum cap bottle
n-Butyllithium, 2.5M in hexane, packaged in resealable septum cap bottle
Lithium Diisopropylamide, 28% (2.2M) in THF/n-heptane, packaged under Argon in resealable septum cap bottles
3-Chloroperoxybenzoic acid, 50-55%, cont. ca 10% 3-chlorobenzoic acid, balance water


 

 

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