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Enzymatic Desymmetrising Redox Reactions for the Asymmetric Synthesis of Biaryl Atropisomers |
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| Authors: | Samantha Staniland Bo Yuan Nelson Giménez‐Agulló Dr Tommaso Marcelli Dr Simon C Willies Dr Damian M Grainger Prof Nicholas J Turner Prof Jonathan Clayden |
| Affiliation: | 1. School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL (UK), Fax: (+44)?161‐275‐4939;2. School of Chemistry, University of Manchester, Manchester Institute of Biotechnology, 131 Princess Street, Manchester M1 7DN (UK), Fax: (+44)?161‐275‐1311;3. Dipartimento di Chimica, Materiali e Ingegneria Chimica “Giulio Natta”, Politecnico di Milano, via Mancinelli 7, 20131 Milano (Italy);4. Johnson Matthey Catalysis and Chiral Technologies, 28 Science Park, Milton Road, Cambridge, CB4 0FP (UK) |
| 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. |
| Keywords: | atropisomerism biaryls biocatalysis galactose oxidase ketoreductase |
