Pd‐Catalyzed [3+6+3+6] Macrocyclizations of Aryl α‐Diazo‐β‐Ketoesters

Thanks to Pd(II)‐catalysis, an efficient synthesis of unsaturated macrocycles is achieved by [3+6+3+6] condensation of cyclic ethers with aryl α‐diazo‐β‐ketoesters. The presence of the electron‐rich aryl ester moieties forbids the use of dirhodium complexes as these diazo decomposition catalysts pro...

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Bibliographic Details
Published in:Advanced synthesis & catalysis 2024-07, Vol.366 (13), p.3029-3035
Main Authors: Zhong, Zhuang, Aguirre, Adiran, Besnard, Céline, Poblador‐Bahamonde, Amalia I., Lacour, Jérôme
Format: Article
Language:English
Subjects:
Aromatic compounds
Catalysis
Catalysts
Chemical synthesis
Decomposition reactions
Diazo decomposition
Ethers
Macrocyclization
Oxonium ylide
Palladium
Palladium(II)-catalysis
Reagents
Rhodium compounds
Rhodium(II)-catalysis
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Summary:Thanks to Pd(II)‐catalysis, an efficient synthesis of unsaturated macrocycles is achieved by [3+6+3+6] condensation of cyclic ethers with aryl α‐diazo‐β‐ketoesters. The presence of the electron‐rich aryl ester moieties forbids the use of dirhodium complexes as these diazo decomposition catalysts provoke unforeseen intermolecular Csp2−H insertion reactions that derail the targeted reactivity. However, with Pd(acac)2, using high concentration conditions (1 M), a variety of 18‐membered macrocycles (16 examples) is afforded with both aryl and alkyl diazo reagents. Catalyst selection for either electrophilic aromatic substitution (Rh) or ylide (Pd) pathways are explained by computational approaches.
ISSN:1615-4150
1615-4169
DOI:10.1002/adsc.202400118