Phosphine‐Catalyzed Difunctionalization of β‐Fluoroalkyl α,β‐Enones: A Direct Approach to β‐Amino α‐Diazo Carbonyl Compounds

An efficient and practical phosphine‐catalyzed vicinal difunctionalization of β‐fluoroalkyl α,β‐enones with TMSN3 has been developed. Using dppb as the catalyst, the reaction worked efficiently to yield various β‐amino α‐diazocarbonyl compounds in high yields (up to 94 %). This work marks the first...

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Bibliographic Details
Published in:Angewandte Chemie 2018-11, Vol.130 (48), p.16013-16017
Main Authors: Wang, Huamin, Zhang, Li, Tu, Youshao, Xiang, Ruiqi, Guo, Yin‐Long, Zhang, Junliang
Format: Article
Language:English
Subjects:
Alkendifunktionalisierung
Azide
Carbonyl compounds
Carbonyls
Catalysis
Chemistry
Diazoverbindungen
Enantiomers
Enone
Intermediates
NMR
Nuclear magnetic resonance
Phosphankatalyse
Phosphine
Reaction intermediates
Yield
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Summary:An efficient and practical phosphine‐catalyzed vicinal difunctionalization of β‐fluoroalkyl α,β‐enones with TMSN3 has been developed. Using dppb as the catalyst, the reaction worked efficiently to yield various β‐amino α‐diazocarbonyl compounds in high yields (up to 94 %). This work marks the first efficient construction of α‐diazocarbonyl compounds by phosphine catalysis. Meanwhile, the asymmetric variant induced by the nucleophilic bifunctional phosphine P4 led to various chiral fluoroalkylated β‐amino α‐diazocarbonyl compounds in high yields and enantioselectivity. NMR and ESI‐MS studies support the existence of the key reaction intermediates. In contrast, β‐azide carbonyl compounds would be furnished in good yields from β‐fluoroalkylated β,β‐disubstituted enones. Effizient und praktisch ist eine Phosphan‐katalysierte vicinale Difunktionalisierung von β‐Fluoralkyl‐α,β‐enonen mit TMSN3. Die vom nukleophilen, difunktionalen Phosphan P4 induzierte, asymmetrische Variante liefert unterschiedliche chirale fluoralkylierte β‐Amino‐α‐diazocarbonyl‐Verbindungen in hohen Ausbeuten und Enantioselektivitäten.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201810253