Overman rearrangement
E749332
The Overman rearrangement is an organic chemical reaction that converts allylic alcohol derivatives into allylic amines via a [3,3]-sigmatropic rearrangement of allylic trichloroacetimidates.
Statements (48)
| Predicate | Object |
|---|---|
| instanceOf |
named reaction
ⓘ
organic reaction ⓘ sigmatropic rearrangement ⓘ |
| applicationField |
medicinal chemistry
ⓘ
total synthesis ⓘ |
| bondReorganization |
cleavage of C–O bond at allylic position
ⓘ
formation of C–N bond at allylic position ⓘ migration of allylic group from oxygen to nitrogen ⓘ |
| converts | allylic alcohol derivatives to allylic amines ⓘ |
| developedBy | Larry E. Overman NERFINISHED ⓘ |
| drivingForce | formation of strong C–N bond and trichloroacetamide ⓘ |
| formsProduct | allylic amines ⓘ |
| functionalGroupTransformation |
allylic alcohol to allylic amine
ⓘ
allylic trichloroacetimidate to trichloroacetamide-protected allylic amine ⓘ |
| keyIntermediate | allylic trichloroacetimidate ⓘ |
| limitation |
requires suitably substituted allylic alcohols
ⓘ
thermal conditions may limit sensitive substrates ⓘ |
| mechanismFeature |
[3,3]-sigmatropic shift
ⓘ
concerted pericyclic process ⓘ |
| namedAfter | Larry E. Overman NERFINISHED ⓘ |
| productHandling | allylic amine often obtained after deprotection of trichloroacetamide ⓘ |
| protectionGroup | trichloroacetyl group on nitrogen ⓘ |
| reactionClass |
pericyclic reaction
ⓘ
rearrangement reaction ⓘ |
| reactionMedium | typically performed in organic solvents ⓘ |
| reactionType | [3,3]-sigmatropic rearrangement ⓘ |
| relatedTo |
Claisen rearrangement
NERFINISHED
ⓘ
Eschenmoser–Claisen rearrangement NERFINISHED ⓘ Ireland–Claisen rearrangement NERFINISHED ⓘ Johnson–Claisen rearrangement NERFINISHED ⓘ |
| requires | formation of trichloroacetimidate from allylic alcohol ⓘ |
| selectivity |
can exhibit high regioselectivity at allylic position
ⓘ
can exhibit high stereoselectivity ⓘ |
| stereochemicalFeature | allylic configuration can be transferred to nitrogen-bearing center ⓘ |
| stereochemicalOutcome | stereospecific under appropriate conditions ⓘ |
| syntheticUse |
construction of nitrogen-containing heterocycles
ⓘ
preparation of allylic amines ⓘ synthesis of alkaloids ⓘ synthesis of natural products ⓘ |
| temperatureRange | usually requires heating ⓘ |
| typicalReagent |
base to form trichloroacetimidate
ⓘ
trichloroacetonitrile ⓘ |
| typicalSolvent |
aromatic solvents
ⓘ
chlorinated solvents ⓘ |
| usedIn | construction of quaternary carbon centers adjacent to nitrogen in some variants ⓘ |
| usesStartingMaterial |
allylic alcohols
ⓘ
allylic trichloroacetimidates ⓘ |
| yearReported | 1974 ⓘ |
Referenced by (3)
Full triples — surface form annotated when it differs from this entity's canonical label.