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Phosphine‐Catalyzed Difunctionalization of β‐Fluoroalkyl α,β‐Enones: A Direct Approach to β‐Amino α‐Diazo Carbonyl Compounds
Author(s) -
Wang Huamin,
Zhang Li,
Tu Youshao,
Xiang Ruiqi,
Guo YinLong,
Zhang Junliang
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201810253
Subject(s) - phosphine , chemistry , diazo , catalysis , nucleophile , azide , bifunctional , organic chemistry , medicinal chemistry , vicinal , yield (engineering) , combinatorial chemistry , materials science , metallurgy
An efficient and practical phosphine‐catalyzed vicinal difunctionalization of β‐fluoroalkyl α,β‐enones with TMSN 3 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.