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Palladium‐Catalyzed Allylic Alkylations without Isomerization—Dream or Reality?
Author(s) -
Kazmaier Uli,
Zumpe Franz L.
Publication year - 2000
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/(sici)1521-3773(20000218)39:4<802::aid-anie802>3.0.co;2-y
Subject(s) - isomerization , palladium , allylic rearrangement , chemistry , nucleophile , stereoselectivity , catalysis , amide , trimethylsilyl cyanide , medicinal chemistry , lithium (medication) , organic chemistry , medicine , endocrinology
Reality catches up with wishful thinking: If highly reactive chelated amino acid ester enolates are used as nucleophiles in palladium‐catalyzed allylic alkylations, the π‐σ‐π isomerization of π‐allyl – palladium intermediates can be suppressed nearly completely. This opens up new synthetic applications, such as stereoselective reactions of ( Z )‐allyl carbonates [Eq. (1); Tfa=trifluoracetyl; LHMDS=lithium bis(trimethylsilyl)amide].