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Overman Rearrangement

Overman rearrangement   Named Reactions in Organic Synthesis

Reaction category:
Pericyclic and photochemical reactions

Other featured pericyclic reactions:

Featured photochemical reactions:

In 1974 the American chemist Larry Overman reported the thermal and mercuric ion catalysed rearrangement of allylic trichloroacetimidates to create the corresponding trichloroacetamides. Subsequently the 1,3-transposition of alcohol and amine functionalities via [3,3]-sigmatropic rearrangement of allylic trichloroacetimidates became known as the Overman rearrangement. The allylic trichloroacetimidates are readily prepared by treating the corresponding alcohols with trichloroacetonitrile in the presence of catalytic amounts of a base such as DBU.

In recent decades the Overman rearrangement has become an important carbon nitrogen bond forming reaction used in many synthesis campaigns. For example during the total synthesis of sphingofungin E by N. Chida and colleagues the stereocenter at C5 was formed using the Overman rearrangement of an allylic trichloroacetimidate derived from diacetone-D-glucose.

 

Mechanism of the Overman rearrangement:

mechanism of overman rearrangment

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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 Overman rearrangement:

Trichloroacetonitrile, 98%
n-Butyllithium, 2.2M in hexane
1,8-Diazabicyclo[5.4.0]undec-7-ene, 99%
Xylenes, mixed, 97+%
Xylenes, ACS, 98.5+% (Assay, isomers plus ethylbenzene

We have many allylic alcohols in our portfolio.


 

 

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