Mechanistic investigation leads to a synthetic improvement in the hydrolytic kinetic resolution of terminal epoxides.
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.
Nielsen
Lars P C
LP
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
Stevenson
Christian P
CP
Blackmond
Donna G
DG
Jacobsen
Eric N
EN
D003035:Cobalt / Q000737:chemistry; D004852:Epoxy Compounds / Q000138:chemical synthesis*; D005029:Ethylenediamines / Q000737:chemistry; D006868:Hydrolysis; D007700:Kinetics; D009942:Organometallic Compounds / Q000737:chemistry
D004852:Epoxy Compounds; D005029:Ethylenediamines; D009942:Organometallic Compounds; D003035:Cobalt; C011452:disalicylaldehyde ethylenediamine