Orchestration of concurrent oxidation and reduction cycles for stereoinversion and deracemisation of sec-alcohols
Orchestration of concurrent oxidation and reduction cycles for stereoinversion and deracemisation of sec-alcohols
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DOI：
10.1021/ja804816a
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发表时间：
2008-10-22
影响因子：
15
通讯作者：
Kroutil, Wolfgang
中科院分区：
文献类型：
--
作者：
Voss, Constance V.;Gruber, Christian C.;Kroutil, Wolfgang
黑与白是对立的，氧化与还原也是对立的。例如，在同一容器中进行仲醇的氧化和相应酮的还原而不分离试剂似乎是不可能的任务。在这里，我们表明，NADP(+) 的氧化辅因子回收和 NADH 的还原再生可以在同一隔室中同时进行，而不会产生明显干扰。再生循环可以彼此相反的方向运行，通过同时进行的对映选择性氧化和不对称还原，使用具有相反立体和辅因子偏好的特定醇脱氢酶，能够将外消旋醇一锅转化为一种对映异构体。因此，通过仔细选择适当的酶，可以在 NADP(+) 回收存在的情况下进行 NADH 回收，以实现总体目标，例如仲醇的去消旋化或立体反转，这代表了与化学密集型 Mitsunobu 反转等效的“绿色”可能概念。
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.