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

详细信息    查看全文

• 作者：Constance V. Voss ; Christian C. Gruber ; Kurt Faber ; Tanja Knaus ; Peter Macheroux ; Wolfgang Kroutil
• 刊名：Journal of the American Chemical Society
• 出版年：2008
• 出版时间：October 22, 2008
• 年：2008
• 卷：130
• 期：42
• 页码：13969-13972
• 全文大小：168K
• 年卷期：v.130,no.42(October 22, 2008)
• ISSN：1520-5126

文摘

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.