Premium
Substrate‐Controlled Palladium‐Catalyzed Allylic Alkylations of Chelated Enolates – Scope and Limitations
Author(s) -
Lindner Thomas,
Kazmaier Uli
Publication year - 2005
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200505140
Subject(s) - chemistry , allylic rearrangement , stereocenter , stereoselectivity , tsuji–trost reaction , palladium , nucleophile , chelation , diastereomer , stereochemistry , catalysis , olefin fiber , medicinal chemistry , enantioselective synthesis , organic chemistry
Chelated enolates of amino acid derivatives were found to be excellent nucleophiles for stereoselective palladium‐catalyzed allylic alkylations via terminal π‐allyl complexes. Neither the olefin geometry (linear substrates) nor the configuration of secondary allylic substrates has an influence on the newly formed stereogenic centre of the amino acid. This is exclusively controlled by the protecting group on the chiral centre. Therefore, depending on the protecting group used, both diastereomeric amino acids can be obtained in a highly stereoselective fashion (up to 96% ds for 1,5 induction) from one allylic alcohol.