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.
All labels observed (1)
| Label | Occurrences |
|---|---|
| Overman rearrangement canonical | 3 |
How this entity was disambiguated
This entity first appeared as the object of triple T8665133 — resolving that mention is where its identity was fixed. The disambiguator weighed these candidate entities and picked the highlighted one (or “None”, minting a new entity). This is how homonymy is resolved: the same surface form can point to different entities.
NED1
Entity disambiguation (via context triple)
gpt-5-mini-2025-08-07
Target entity: Overman rearrangement Context triple: [Larry E. Overman, knownFor, Overman rearrangement]
-
A.
Stork–Danheiser rearrangement
The Stork–Danheiser rearrangement is an organic reaction that transforms certain allylic alcohol derivatives into rearranged carbonyl compounds via a sigmatropic shift, widely used in complex molecule synthesis.
-
B.
Eschenmoser–Claisen rearrangement
The Eschenmoser–Claisen rearrangement is a variant of the Claisen rearrangement in organic chemistry that converts allylic alcohols and amides into γ,δ-unsaturated carbonyl compounds via a [3,3]-sigmatropic rearrangement.
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C.
Barton reaction
The Barton reaction is an organic photochemical transformation that converts nitrite esters into δ-nitroso alcohols via intramolecular hydrogen abstraction and radical rearrangement.
-
D.
Robinson annulation reaction
The Robinson annulation reaction is a classic organic chemistry transformation that forms six-membered rings by combining a Michael addition with an intramolecular aldol condensation, widely used in the synthesis of complex cyclic molecules and natural products.
-
E.
Norrish reaction
The Norrish reaction is a photochemical process in organic chemistry involving the cleavage and rearrangement of carbonyl compounds under ultraviolet light, fundamental to understanding photodegradation and radical mechanisms.
- F. None of above. chosen
- G. Unsure - the case is ambiguous/there is not enough information to decide.
NED2
Entity disambiguation (via description)
gpt-5-mini-2025-08-07
Target entity: Overman rearrangement Target entity description: 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.
-
A.
Stork–Danheiser rearrangement
The Stork–Danheiser rearrangement is an organic reaction that transforms certain allylic alcohol derivatives into rearranged carbonyl compounds via a sigmatropic shift, widely used in complex molecule synthesis.
-
B.
Eschenmoser–Claisen rearrangement
The Eschenmoser–Claisen rearrangement is a variant of the Claisen rearrangement in organic chemistry that converts allylic alcohols and amides into γ,δ-unsaturated carbonyl compounds via a [3,3]-sigmatropic rearrangement.
-
C.
Barton reaction
The Barton reaction is an organic photochemical transformation that converts nitrite esters into δ-nitroso alcohols via intramolecular hydrogen abstraction and radical rearrangement.
-
D.
Robinson annulation reaction
The Robinson annulation reaction is a classic organic chemistry transformation that forms six-membered rings by combining a Michael addition with an intramolecular aldol condensation, widely used in the synthesis of complex cyclic molecules and natural products.
-
E.
Norrish reaction
The Norrish reaction is a photochemical process in organic chemistry involving the cleavage and rearrangement of carbonyl compounds under ultraviolet light, fundamental to understanding photodegradation and radical mechanisms.
- F. None of above. chosen
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 ⓘ |
| 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 ⓘ |
| 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
ⓘ
Eschenmoser–Claisen rearrangement ⓘ Ireland–Claisen rearrangement ⓘ Johnson–Claisen rearrangement ⓘ
linked to:
Claisen rearrangement
|
| 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 ⓘ |
How these facts were elicited
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Instruction
You are a knowledge base construction expert. Given a subject entity and a description of it, return factual statements that you know for the subject as a JSON list of dictionaries(triples), where keys must be "subject", "predicate" and "object". The number of facts may be very high, between 25 to 50 or more, for very popular subjects. For less popular subjects, the number of facts can be very low, like 5 or 10. # Requirements - If you don't know the subject at all, return an empty list. - If the subject is not a named entity, return an empty list. - Include at least one triple where predicate is "instanceOf". - Do not get too wordy. - Separate several objects into multiple triples with one object.
Input
Subject: Overman rearrangement Description of subject: 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.
Referenced by (3)
Full triples — surface form annotated when it differs from this entity's canonical label.