Prev. Article Next Article Table of Contents

Article

Orchestration of Concurrent Oxidation and Reduction Cycles for Stereoinversion and Deracemisation of sec-Alcohols

Supporting Info

Constance V. Voss^†, Christian C. Gruber^†, Kurt Faber^†, Tanja Knaus^‡, Peter Macheroux^‡ and Wolfgang Kroutil*^†

Department of Chemistry, Organic and Bioorganic Chemistry, University of Graz, Heinrichstrasse 28, A-8010 Graz, Austria, and Institute of Biochemistry, Graz University of Technology, Petersgasse 12, 8010 Graz, Austria

J. Am. Chem. Soc., 2008, 130 (42), pp 13969–13972

DOI: 10.1021/ja804816a

Publication Date (Web): September 27, 2008

†

University of Graz.

‡

Graz University of Technology.

Abstract

Black and white are opposites as are oxidation and reduction. Performing an oxidation, for example, of a sec-alcohol and a reduction of the corresponding ketone in the same vessel without separation of the reagents seems to be an impossible task. Here we show that oxidative cofactor recycling of NADP⁺ and reductive regeneration of NADH can be performed simultaneously in the same compartment without significant interference. Regeneration cycles can be run in opposing directions beside each other enabling one-pot transformation of racemic alcohols to one enantiomer via concurrent enantioselective oxidation and asymmetric reduction employing defined alcohol dehydrogenases with opposite stereo- and cofactor-preference. Thus, by careful selection of appropriate enzymes, NADH recycling can be performed in the presence of NADP⁺ recycling to achieve overall, for example, deracemisation of sec-alcohols or stereoinversion representing a possible concept for a “green” equivalent to the chemical-intensive Mitsunobu inversion.

View: Full Text HTML | Hi-Res PDF | PDF w/ Links