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Umpolung of Carbonyl Groups as Alkyl Organometallic Reagent Surrogates for Palladium‐Catalyzed Allylic Alkylation
Author(s) -
Zhu Dianhu,
Lv Leiyang,
Li ChenChen,
Ung Sosthene,
Gao Jian,
Li ChaoJun
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.201809112
Subject(s) - umpolung , nucleophile , chemistry , alkyl , palladium , electrophile , allylic rearrangement , regioselectivity , alkylation , reagent , catalysis , organic chemistry , aryl , tsuji–trost reaction , carbanion , combinatorial chemistry , medicinal chemistry
Palladium‐catalyzed allylic alkylation of nonstabilized carbon nucleophiles is difficult and remains a major challenge. Reported here is a highly chemo‐ and regioselective direct palladium‐catalyzed C‐allylation of hydrazones, generated from carbonyls, as a source of umpolung unstabilized alkyl carbanions and surrogates of alkyl organometallic reagents. Contrary to classical allylation techniques, this umpolung reaction utilizes hydrazones prepared not only from aryl aldehydes but also from alkyl aldehydes and ketones as renewable feedstocks. This strategy complements the palladium‐catalyzed coupling of unstabilized nucleophiles with allylic electrophiles by providing an efficient and selective catalytic alternative to the traditional use of highly reactive alkyl organometallic reagents.