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Enantioselective Construction of All‐Carbon Quaternary Stereocenters Using Palladium‐Catalyzed Asymmetric Allylic Alkylation of γ‐Acetoxy‐α,β‐unsaturated Carbonyl Compounds
Author(s) -
Nemoto Tetsuhiro,
Fukuda Tomoaki,
Matsumoto Takayoshi,
Hitomi Tsukasa,
Hamada Yasumasa
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.200505149
Subject(s) - stereocenter , enantioselective synthesis , tsuji–trost reaction , chemistry , alkylation , nucleophile , allylic rearrangement , catalysis , organic chemistry , palladium , quaternary carbon , medicinal chemistry
We have successfully demonstrated that γ‐acetoxy‐α,β‐unsaturated carbonyl compounds are useful starting materials for Pd‐catalyzed asymmetric allylic alkylation to construct all‐carbon quaternary stereocenters. With the use of 2–5 mol % of Pd catalyst and 4–10 mol % of P‐chirogenic diaminophosphine oxides, asymmetric allylic alkylation of γ‐acetoxy‐α,β‐unsaturated carbonyl compounds with various prochiral nucleophiles derived from cyclic β‐keto esters proceeded in the presence of Zn(OAc) 2 , providing the corresponding products with an all‐carbon quaternary stereocenter in up to 95% ee.