title: Mechanistic investigation leads to a synthetic improvement in the hydrolytic kinetic resolution of terminal epoxides.
abstract: The mechanism of the hydrolytic kinetic resolution (HKR) of terminal epoxides was investigated by kinetic analysis using reaction calorimetry. The chiral (salen)Co-X complex (X = OAc, OTs, Cl) undergoes irreversible conversion to (salen)Co-OH during the course of the HKR and thus serves as both precatalyst and cocatalyst in a cooperative bimetallic catalytic mechanism. This insight led to the identification of more active catalysts for the HKR of synthetically useful terminal epoxides.
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
authors.forename: Lars P C
authors.initials: LP
authors.lastname: Nielsen
authors.forename: Christian P
authors.initials: CP
authors.lastname: Stevenson
authors.forename: Donna G
authors.initials: DG
authors.lastname: Blackmond
authors.forename: Eric N
authors.initials: EN
authors.lastname: Jacobsen
mesh_terms: D003035:Cobalt / Q000737:chemistry; D004852:Epoxy Compounds / Q000138:chemical synthesis*; D005029:Ethylenediamines / Q000737:chemistry; D006868:Hydrolysis; D007700:Kinetics; D009942:Organometallic Compounds / Q000737:chemistry
chemical_list: D004852:Epoxy Compounds; D005029:Ethylenediamines; D009942:Organometallic Compounds; D003035:Cobalt; C011452:disalicylaldehyde ethylenediamine