A facile approach is introduced here for the synthesis of rare ketoses from glycerol and d-/l-glyceraldehyde (d-/l-GA). The reactions were carried out in a one-pot multienzyme fashion in which the only carbon source is glycerol. In the enzymatic cascade, glycerol is phosphorylated and then oxidized at C2 to afford dihydroxyacetone phosphate (DHAP), the key donor for enzymatic aldol reaction. Meanwhile, the primary alcohol of glycerol is also oxidized to give the acceptor molecule GA in situ (d- or l-isomer could be formed stereospecifically with either alditol oxidase or horse liver alcohol dehydrogenase). Different DHAP-dependent aldolases were used to generate the aldol adducts (rare ketohexose phosphates) with various stereoconfigurations and diastereomeric ratios. It is worth noting that the enzyme that catalyzes the phosphorylation reaction in the first step could also help recycle the phosphate in the last step to provide free rare sugar molecules. This study provides a useful method for rare ketose synthesis on a 100 mg to g scale, starting from relatively inexpensive materials which solved the problem of supplying both glycerol 3-phosphate and GA in our previous work. It also demonstrates an example of green synthesis due to highly efficient carbon usage and recycling of cofactors.

中文翻译：

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从甘油一锅法合成稀有酮酶。

本文介绍了一种从甘油和d- / l-甘油醛（d- / l-GA）合成稀有酮糖的简便方法。反应以一锅多酶的方式进行，其中唯一的碳源是甘油。在酶促级联反应中，甘油被磷酸化，然后在C2氧化，得到磷酸二羟基丙酮磷酸酯（DHAP），这是酶促醛缩反应的关键供体。同时，甘油的伯醇也被氧化以原位产生受体分子GA（d-或l-异构体可以用糖醇氧化酶或马肝醇脱氢酶立体定向形成）。使用不同的DHAP依赖的醛缩酶来生成具有各种立体构型和非对映异构体比例的醛醇加合物（稀有酮己糖磷酸酯）。值得注意的是，第一步中催化磷酸化反应的酶也可以帮助最后一步中的磷酸盐再循环，从而提供游离的稀有糖分子。这项研究提供了一种有用的方法，可以从相对便宜的材料开始，以100 mg到g的规模进行稀有的酮糖合成，这解决了我们以前的工作中同时提供3-磷酸甘油和GA的问题。由于高效的碳使用和辅助因子的循环利用，它还展示了绿色合成的示例。从相对便宜的材料开始，在我们以前的工作中解决了同时供应3-磷酸甘油和GA的问题。由于高效的碳使用和辅助因子的循环利用，它还展示了绿色合成的示例。从相对便宜的材料开始，在我们以前的工作中解决了同时供应3-磷酸甘油和GA的问题。由于高效的碳使用和辅助因子的循环利用，它还展示了绿色合成的示例。