Palladium‐Catalyzed Dearomative syn‐1,4‐Oxyamination

A palladium‐catalyzed dearomative syn‐1,4‐oxyamination protocol using non‐activated arenes has been developed. This one‐pot procedure utilizes arenophile chemistry, and the corresponding para‐cycloadducts are treated with oxygen nucleophiles via formal allylic substitution, providing direct access t...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2019-10, Vol.58 (44), p.15762-15766
Main Authors: Tang, Conghui, Okumura, Mikiko, Deng, Hejun, Sarlah, David
Format: Article
Language:English
Subjects:
Alcohols
Allyl Compounds - chemistry
Amines - chemical synthesis
Amines - chemistry
arene
arenophile
Aromatic compounds
Benzyl alcohol
Catalysis
Cycloaddition Reaction
dearomatization
Enantiomers
Molecular Structure
Nucleophiles
Organic chemistry
Oximes
oxyamination
Oxygen - chemistry
Palladium
Palladium - chemistry
photochemistry
Stereoisomerism
Substitution reactions
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Summary:A palladium‐catalyzed dearomative syn‐1,4‐oxyamination protocol using non‐activated arenes has been developed. This one‐pot procedure utilizes arenophile chemistry, and the corresponding para‐cycloadducts are treated with oxygen nucleophiles via formal allylic substitution, providing direct access to syn‐1,4‐oxyaminated products. The reaction conditions permit a range of arenes, as well as different O‐nucleophiles, such as oximes and benzyl alcohols. Moreover, this process was established in an asymmetric fashion, delivering products with high enantioselectivity. The dearomatized products are amenable to a multitude of further derivatizations ranging from olefin chemistry to C−H activation, giving rise to a diverse set of new functionalities. Overall, this dearomative functionalization offers rapid and controlled formation of molecular complexity, enabling straightforward access to functionalized small molecules from simple and readily available arenes. Escape from flatland: A dearomative strategy is reported based on combination of arenophile chemistry and Pd catalysis. Non‐activated arenes were readily converted into the corresponding syn‐1,4‐oxyaminated products using oximes or benzyl alcohols as O‐nucleophiles. This process delivers products with an exclusive diastereoselectivity, amenable to myriad of further elaborations.
ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.201909838