title: Palladium(II)-catalyzed oxidative cyclization of allylic tosylcarbamates: scope, derivatization, and mechanistic aspects.
abstract: 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.
authors.affiliation: Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 106 91, Stockholm, Sweden.
authors.forename: Antoine
authors.initials: A
authors.lastname: Joosten
authors.forename: Andreas K Å
authors.initials: AK
authors.lastname: Persson
authors.forename: Renaud
authors.initials: R
authors.lastname: Millet
authors.forename: Magnus T
authors.initials: MT
authors.lastname: Johnson
authors.forename: Jan-E
authors.initials: JE
authors.lastname: Bäckvall
mesh_terms: D000498:Allyl Compounds / Q000737:chemistry*; D002254:Carbonates / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D003500:Cyclization; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D023303:Oxazolidinones / Q000138:chemical synthesis* / Q000737:chemistry; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry*
chemical_list: D000498:Allyl Compounds; D002254:Carbonates; D009942:Organometallic Compounds; D023303:Oxazolidinones; D010165:Palladium