title: Asymmetric synthesis of chloroisothreonine derivatives via syn-stereoselective Mannich-type additions across N-sulfinyl-α-chloroimines.
abstract: Mannich-type reactions of O-Boc glycolic esters across chiral N-sulfinyl-α-chloroaldimines resulted in the efficient and syn-stereoselective synthesis of new γ-chloro-α-hydroxy-β-amino esters (dr > 99 : 1). The α-coordinating ability of the chlorine atom was of great importance for the diastereoselectivity of the Mannich-type reaction and overruled the chelation of the sulfinyl oxygen with the lithium ion of the incoming E-enolate in the transition state model. These novel chloroisothreonine derivatives proved to be excellent building blocks in asymmetric synthesis of novel syn-β,γ-aziridino-α-hydroxy esters and biologically relevant trans-oxazolidinone carboxylic esters.
authors.affiliation: Department of Sustainable Organic Chemistry and Technology, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, B-9000 Ghent, Belgium. Sven.Mangelinckx@UGent.be.
authors.forename: Gert
authors.initials: G
authors.lastname: Callebaut
authors.forename: Filip
authors.initials: F
authors.lastname: Colpaert
authors.forename: Melinda
authors.initials: M
authors.lastname: Nonn
authors.forename: Loránd
authors.initials: L
authors.lastname: Kiss
authors.forename: Reijo
authors.initials: R
authors.lastname: Sillanpää
authors.forename: Karl W
authors.initials: KW
authors.lastname: Törnroos
authors.forename: Ferenc
authors.initials: F
authors.lastname: Fülöp
authors.forename: Norbert
authors.initials: N
authors.lastname: De Kimpe
authors.forename: Sven
authors.initials: S
authors.lastname: Mangelinckx
mesh_terms: D018360:Crystallography, X-Ray; D004952:Esters / Q000138:chemical synthesis / Q000737:chemistry; D006843:Hydrocarbons, Chlorinated / Q000737:chemistry*; D007097:Imines / Q000737:chemistry*; D008352:Mannich Bases / Q000737:chemistry*; D008958:Models, Molecular; D013237:Stereoisomerism; D013912:Threonine / Q000031:analogs & derivatives* / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D004952:Esters; D006843:Hydrocarbons, Chlorinated; D007097:Imines; D008352:Mannich Bases; C531274:alpha-chloroimine; D013912:Threonine