Eschenmoser–Claisen rearrangement
E398759
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.
All labels observed (1)
| Label | Occurrences |
|---|---|
| Eschenmoser–Claisen rearrangement canonical | 5 |
How this entity was disambiguated
This entity first appeared as the object of triple T3935407 — 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: Eschenmoser–Claisen rearrangement Context triple: [Albert Eschenmoser, knownFor, Eschenmoser–Claisen rearrangement]
-
A.
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.
-
B.
Barton–McCombie deoxygenation
Barton–McCombie deoxygenation is an organic chemistry reaction that converts alcohols into the corresponding hydrocarbons via radical-mediated removal of the hydroxyl group.
-
C.
Buchwald–Hartwig amination
The Buchwald–Hartwig amination is a palladium-catalyzed cross-coupling reaction that forms carbon–nitrogen bonds by coupling aryl (or vinyl) halides with amines, widely used in the synthesis of pharmaceuticals and fine chemicals.
-
D.
Suzuki coupling
Suzuki coupling is a widely used palladium-catalyzed cross-coupling reaction that forms carbon–carbon bonds between organoboron compounds and organic halides, fundamental in organic synthesis and pharmaceutical chemistry.
-
E.
Sharpless epoxidation
Sharpless epoxidation is a landmark asymmetric oxidation reaction in organic chemistry that enables the enantioselective conversion of allylic alcohols to epoxides using chiral catalysts.
- 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: Eschenmoser–Claisen rearrangement Target entity description: 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.
-
A.
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.
-
B.
Barton–McCombie deoxygenation
Barton–McCombie deoxygenation is an organic chemistry reaction that converts alcohols into the corresponding hydrocarbons via radical-mediated removal of the hydroxyl group.
-
C.
Buchwald–Hartwig amination
The Buchwald–Hartwig amination is a palladium-catalyzed cross-coupling reaction that forms carbon–nitrogen bonds by coupling aryl (or vinyl) halides with amines, widely used in the synthesis of pharmaceuticals and fine chemicals.
-
D.
Suzuki coupling
Suzuki coupling is a widely used palladium-catalyzed cross-coupling reaction that forms carbon–carbon bonds between organoboron compounds and organic halides, fundamental in organic synthesis and pharmaceutical chemistry.
-
E.
Sharpless epoxidation
Sharpless epoxidation is a landmark asymmetric oxidation reaction in organic chemistry that enables the enantioselective conversion of allylic alcohols to epoxides using chiral catalysts.
- F. None of above. chosen
Statements (44)
| Predicate | Object |
|---|---|
| instanceOf |
Claisen rearrangement variant
ⓘ
[3,3]-sigmatropic rearrangement ⓘ organic reaction ⓘ |
| application |
natural product synthesis
ⓘ
stereocontrolled C–C bond formation ⓘ synthesis of γ,δ-unsaturated carbonyl building blocks ⓘ |
| bondCleavage | C–O bond cleavage in imidate or amide acetal ⓘ |
| bondFormation | new C–C bond at γ-position ⓘ |
| bondReorganization | [3,3]-sigmatropic shift ⓘ |
| category | named reaction in organic chemistry ⓘ |
| conditions | thermal conditions ⓘ |
| developedBy | Albert Eschenmoser ⓘ |
| drivingForce | formation of conjugated carbonyl system ⓘ |
| field | organic chemistry ⓘ |
| governingRules |
Woodward–Hoffmann rules for pericyclic reactions
ⓘ
linked to:
Woodward–Hoffmann rules
|
| keyIntermediate |
amide acetal
ⓘ
imidate ester ⓘ |
| limitation | requires formation of suitable imidate or amide acetal precursor ⓘ |
| mechanism | concerted pericyclic process ⓘ |
| namedAfter | Albert Eschenmoser ⓘ |
| notation | [3,3]-sigmatropic rearrangement of imidates or amide acetals ⓘ |
| product |
γ,δ-unsaturated amides
ⓘ
γ,δ-unsaturated carbonyl compounds ⓘ γ,δ-unsaturated esters ⓘ |
| reactionClass |
Claisen-type rearrangement
ⓘ
linked to:
Ireland–Claisen rearrangement
|
| reactionType |
pericyclic reaction
ⓘ
sigmatropic rearrangement ⓘ |
| relatedTo |
Claisen rearrangement
ⓘ
Ireland–Claisen rearrangement ⓘ Johnson–Claisen rearrangement ⓘ
linked to:
Claisen rearrangement
Overman rearrangement ⓘ |
| scope | broad range of allylic substrates ⓘ |
| selectivity | predictable regiochemistry ⓘ |
| startingMaterial |
allylic alcohol-derived amides
ⓘ
allylic alcohol-derived imidates ⓘ allylic alcohols ⓘ allylic amides ⓘ |
| stereochemicalOutcome | chirality transfer from allylic center ⓘ |
| stereochemistry | stereospecific rearrangement ⓘ |
| thermodynamicFeature | irreversible under typical conditions ⓘ |
| transitionState | six-membered cyclic transition state ⓘ |
| usesReagent |
N,N-dialkylformamides or related amide acetals
ⓘ
orthoformates or formamides to generate imidates ⓘ |
| yearDescribedApprox | 1960s ⓘ |
How these facts were elicited
The pipeline generated the facts above by prompting gpt-5.1 with this entity's name + description and the instruction below.
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: Eschenmoser–Claisen rearrangement Description of subject: 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.
Referenced by (5)
Full triples — surface form annotated when it differs from this entity's canonical label.