Metal-catalyzed asymmetric oxidations.
Recent advances in enantioselective metal-catalyzed oxidations are presented. Two transformations are discussed in detail: (a) asymmetric Baeyer-Villiger reactions of racemic and prochiral cyclic ketones giving optically active lactones, and (b) sulfide oxidations affording enantiomerically enriched sulfoxides. For both reactions, new metal/ligand combinations have been introduced which allow catalysis of these reactions with high enantioselectivities. For some substrates, the ee-values are above 90%. As previously demonstrated, sulfoxides can be iminated to give the corresponding sulfoximines. Under appropriate reaction conditions, this transformation is stereospecific and enantiopure sulfoximines are obtained. These highly oxidized sulfur reagents have now been modified to give beta-amino acid analogues which may be incorporated into peptides. Two variants have been realized: either the sulfoximine-containing pseudo-amino acids are connected with standard alpha-amino acids to give mixed pseudopeptides, or the sulfoxime units are mutually attached to give homooligomers, which can be regarded as beta-peptide analogues.
Bolm
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Institut für Organische Chemie der RWTH Aachen, Professor-Pirlet-Str.1, D-52056 Aachen, Germany. Carsten.Bolm@oc.RWTH-Aachen.de
D000596:Amino Acids / Q000737:chemistry; D002384:Catalysis; D006801:Humans; D007097:Imines / Q000737:chemistry; D007659:Ketones / Q000737:chemistry; D007783:Lactones / Q000737:chemistry; D008024:Ligands; D008670:Metals / Q000737:chemistry*; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D013440:Sulfides / Q000737:chemistry; D013454:Sulfoxides / Q000737:chemistry
D000596:Amino Acids; D007097:Imines; D007659:Ketones; D007783:Lactones; D008024:Ligands; D008670:Metals; D013440:Sulfides; D013454:Sulfoxides