Metal complex amino acid synthons: syntheses, structures and stereoselective reactions of (iminoacetato)cobalt(III) complexes.
dc.contributor.author | Bendahl, Lars | |
dc.contributor.author | Hammershoi, Anders | |
dc.contributor.author | Jensen, Dan | |
dc.contributor.author | Larsen, Sine | |
dc.contributor.author | Riisager, Anders | |
dc.contributor.author | Sargeson, Alan | |
dc.contributor.author | Sorensen, Henning | |
dc.date.accessioned | 2015-12-13T22:23:00Z | |
dc.date.available | 2015-12-13T22:23:00Z | |
dc.date.issued | 2002 | |
dc.date.updated | 2015-12-11T08:01:59Z | |
dc.description.abstract | Amino acid anions (AAO-) chelated to cobalt(III) in [(en)2Co(AAO)](O3SCF3)2 (AA = Gly, Sar, Ala and Glu) were selectively oxidized to their imine derivatives by a new general procedure utilizing PBr3 and N-bromosuccinimide in dmf. The new iminoacetato complexes, Λ- and Δ-[(en)2Co(O2CCH=NH)](O3SCF 3)2, constitute chiral glycine equivalents which can serve as synthons for stereoselective α-amino acid synthesis. In alkaline EtOH, quantitative addition of CH2(COMe)2, CH2(CO2Et)2 or MeCOCH2CO2Et to the imine of the iminoacetate ligand initially produced both diastereomers of the product α-amino acid cobalt(III) complexes. However, subsequent crystallization-induced asymmetric transformations in the heterogeneous reaction mixtures led to better than 90% excess of a single diastereomer after five days, and the diastereopure product triflate salts were obtained after recrystallization. Both enantiomers of isotopically substituted (3-13C, 98%)aspartic acid were produced by facile synthesis from Δ-[(en)2Co(O2CCH=NH)](O3SCF 3)2 and diethyl (2-13C)malonate. The new N-methyliminoacetato complex, rac-[(en)2Co(O2CCH=NMe)](O3SCF3) 2, also yielded to imine addition reactions providing a route to the α-N-methylamino acid subclass. The molecular structures of the new imine complexes, Λ-(+)578-[(en)2Co(O2CCH=NH)]Br 2·H2O and rac-[(en)2Co(O2CCH=NMe)]S2O6 ·1.5H2O, and the diethyl carboxy-aspartate addition product, (ΛS,ΔR)-[(en)2Co{O2CCH(CH(CO2 Et)2)NH2}](ClO4)2, were determined by X-ray crystallography. | |
dc.identifier.issn | 1477-9226 | |
dc.identifier.uri | http://hdl.handle.net/1885/72559 | |
dc.publisher | Royal Society of Chemistry | |
dc.source | Dalton Transactions | |
dc.subject | Keywords: Chelation; Complexation; Crystallization; Derivatives; Molecular structure; Oxidation; Stereochemistry; Synthesis (chemical); X ray crystallography; Stereoselective reactions; Amino acids | |
dc.title | Metal complex amino acid synthons: syntheses, structures and stereoselective reactions of (iminoacetato)cobalt(III) complexes. | |
dc.type | Journal article | |
local.bibliographicCitation.lastpage | 3064 | |
local.bibliographicCitation.startpage | 3054 | |
local.contributor.affiliation | Bendahl, Lars, University of Copenhagen | |
local.contributor.affiliation | Hammershoi, Anders, University of Copenhagen | |
local.contributor.affiliation | Jensen, Dan, University of Copenhagen | |
local.contributor.affiliation | Larsen, Sine, University of Copenhagen | |
local.contributor.affiliation | Riisager, Anders, University of Copenhagen | |
local.contributor.affiliation | Sargeson, Alan, College of Physical and Mathematical Sciences, ANU | |
local.contributor.affiliation | Sorensen, Henning, University of Copenhagen | |
local.contributor.authoremail | u5800192@anu.edu.au | |
local.contributor.authoruid | Sargeson, Alan, u5800192 | |
local.description.notes | Imported from ARIES | |
local.description.refereed | Yes | |
local.identifier.absfor | 039904 - Organometallic Chemistry | |
local.identifier.ariespublication | MigratedxPub3306 | |
local.identifier.scopusID | 2-s2.0-0035982507 | |
local.identifier.uidSubmittedBy | Migrated | |
local.type.status | Published Version |