title: Enzymatic desymmetrising redox reactions for the asymmetric synthesis of biaryl atropisomers.
abstract: Atropisomeric biaryls carrying ortho-hydroxymethyl and formyl groups were made enantioselectively by desymmetrisation of dialdehyde or diol substrates. The oxidation of the symmetrical diol substrates was achieved using a variant of galactose oxidase (GOase), and the reduction of the dialdehydes using a panel of ketoreductases. Either M or P enantiomers of the products could be formed, with absolute configurations assigned by time-dependent DFT calculations of circular dichroism spectra. The differing selectivities observed with different biaryl structures offer an insight into the detailed structure of the active site of the GOase enzyme.
authors.affiliation: School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL (UK), Fax: (+44) 161-275-4939.
authors.forename: Samantha
authors.initials: S
authors.lastname: Staniland
authors.forename: Bo
authors.initials: B
authors.lastname: Yuan
authors.forename: Nelson
authors.initials: N
authors.lastname: Giménez-Agulló
authors.forename: Tommaso
authors.initials: T
authors.lastname: Marcelli
authors.forename: Simon C
authors.initials: SC
authors.lastname: Willies
authors.forename: Damian M
authors.initials: DM
authors.lastname: Grainger
authors.forename: Nicholas J
authors.initials: NJ
authors.lastname: Turner
authors.forename: Jonathan
authors.initials: J
authors.lastname: Clayden
mesh_terms: D000447:Aldehydes / Q000737:chemistry / Q000378:metabolism; D055162:Biocatalysis; D020134:Catalytic Domain; D002942:Circular Dichroism; D005692:Galactose Oxidase / Q000737:chemistry / Q000235:genetics / Q000378:metabolism*; D008958:Models, Molecular; D009154:Mutation; D010084:Oxidation-Reduction; D010088:Oxidoreductases / Q000737:chemistry / Q000378:metabolism*; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D010088:Oxidoreductases; D005692:Galactose Oxidase
keywords: atropisomerism; biaryls; biocatalysis; galactose oxidase; ketoreductase