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Palladium(II)‐Catalyzed Oxidative Cyclization of Allylic Tosylcarbamates: Scope, Derivatization, and Mechanistic Aspects
Author(s) -
Joosten Antoine,
Persson Andreas K. Å.,
Millet Renaud,
Johnson Magnus T.,
Bäckvall JanE.
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201202359
Subject(s) - allylic rearrangement , chemistry , catalysis , palladium , oxidative addition , wacker process , combinatorial chemistry , olefin fiber , oxidative phosphorylation , kinetic resolution , organic chemistry , metathesis , medicinal chemistry , polymerization , enantioselective synthesis , biochemistry , polymer
A highly selective oxidative palladium(II)‐catalyzed (Wacker‐type) cyclization of readily available allylic tosylcarbamates is reported. This operationally simple catalytic reaction furnishes tosyl‐protected vinyl‐oxazolidinones, common precursors to syn ‐1,2‐amino alcohols, in high yield and excellent diasteroselectivity (>20:1). It is demonstrated that both stoichiometric amounts of benzoquinone (BQ) as well as aerobic reoxidation (molecular oxygen) is suitable for this transformation. The title reaction is shown to proceed through overall trans ‐amidopalladation of the olefin followed by β‐hydride elimination. This process is scalable and the products are suitable for a range of subsequent transformations such as: kinetic resolution (KR) and oxidative Heck‐, Wacker‐, and metathesis reactions.