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An Efficient Protocol for the Palladium‐Catalyzed Asymmetric Decarboxylative Allylic Alkylation Using Low Palladium Concentrations and a Palladium(II) Precatalyst
Author(s) -
Marziale Alexander N.,
Duquette Douglas C.,
Craig Robert A.,
Kim Kelly E.,
Liniger Marc,
Numajiri Yoshitaka,
Stoltz Brian M.
Publication year - 2015
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.201500253
Subject(s) - palladium , tsuji–trost reaction , chemistry , catalysis , enantioselective synthesis , alkylation , allylic rearrangement , combinatorial chemistry , organic chemistry
Enantioselective catalytic allylic alkylation for the synthesis of 2‐alkyl‐2‐allylcycloalkanones and 3,3‐disubstituted pyrrolidinones, piperidinones and piperazinones has been previously reported by our laboratory. The efficient construction of chiral all‐carbon quaternary centers by allylic alkylation was previously achieved with a catalyst derived in situ from zero‐valent palladium sources and chiral phosphinooxazoline (PHOX) ligands. We now report an improved reaction protocol with broad applicability among different substrate classes in industry‐compatible reaction media using loadings of palladium(II) acetate as low as 0.075 mol% and the readily available chiral PHOX ligands. The novel and highly efficient procedure enables facile scale‐up of the reaction in an economical and sustainable fashion.