Stereoselective palladium-catalyzed functionalization of homoallylic alcohols: a convenient synthesis of Di- and tri-substituted isoxazolidines and β-Amino-δ-hydroxy esters

Malkov, A.V., Barłóg, M., Miller-Potucká, L., Kabeshov, M.A., Farrugia, L.J. and Kočovský, P. (2012) Stereoselective palladium-catalyzed functionalization of homoallylic alcohols: a convenient synthesis of Di- and tri-substituted isoxazolidines and β-Amino-δ-hydroxy esters. Chemistry: A European Journal, 18(22), pp. 6873-6884. (doi:10.1002/chem.201102716)

Full text not currently available from Enlighten.

Publisher's URL: http://dx.doi.org/10.1002/chem.201102716

Abstract

Enantiopure, Boc-protected alkoxyamines 12 and 13, derived from the readily available homoallylic alcohols 4 via a reaction that involves either inversion or retention of configuration, undergo a diastereoselective Pd-catalyzed ring-closing carbonylative amidation to produce isoxazolidines 16/17 (≤50:1 diastereoisomer ratio (d.r.)) that can be readily converted into the N-Boc-protected esters of β-amino-δ-hydroxy acids and their γ-substituted homologues 37. The key carbonylative cyclization proceeds through an unusual syn addition of the palladium and the nitrogen nucleophile across the C[DOUBLE BOND]C bond (19→21), as revealed by the reaction of 15, which afforded isoxazolidine 18 with high diastereoselectivity.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Malkov, Dr Andrei and Farrugia, Dr Louis and Kabeshov, Mr Mikhail
Authors: Malkov, A.V., Barłóg, M., Miller-Potucká, L., Kabeshov, M.A., Farrugia, L.J., and Kočovský, P.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Chemistry: A European Journal
Journal Abbr.:Chem. Eur J.
ISSN:0947-6539
ISSN (Online):1521-3765

University Staff: Request a correction | Enlighten Editors: Update this record

Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
431361Generation of singlet oxygen mediated by silicon nanoassemblies for novel organic catalytic reactionsPavel KocovskyEngineering & Physical Sciences Research Council (EPSRC)EP/E011179/1CHEM - CHEMISTRY