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Gas-phase sugar formation using hydroxymethylene as the reactive formaldehyde isomer
Nature Chemistry ( IF 21.8 ) Pub Date : 2018-09-10 , DOI: 10.1038/s41557-018-0128-2
André K. Eckhardt , Michael M. Linden , Raffael C. Wende , Bastian Bernhardt , Peter R. Schreiner

Carbohydrates (CH2O)n are the formal adducts of carbon (atoms) to water with a repeating unit that structurally resembles H–C̈–OH (hydroxymethylene). Although hydroxymethylene has been suggested as a building block for sugar formation, it is a reactive species that had escaped detection until recently. Here we demonstrate that formaldehyde reacts with its isomer hydroxymethylene to give glycolaldehyde in a nearly barrierless reaction. This carbonyl–ene-type transformation operates in the absence of base and solvent at cryogenic temperatures similar to those found in extraterrestrial environments or interstellar clouds. Hydroxymethylene acts as a building block for an iterative sugar synthesis, as we demonstrate through the formation of the triose glyceraldehyde. The thermodynamically preferred ketose dihydroxyacetone does not form, and the formation of further branched sugars in the iterative synthesis presented here is unlikely. The results therefore provide a link between the well-known formose (Butlerow) reaction and sugar formation under non-aqueous conditions.



中文翻译:

使用羟甲基作为反应性甲醛异构体的气相糖形成

碳水化合物(CH 2 O)n是碳(原子)与水的形式加合物,其重复单元在结构上类似于H–C̈–OH(羟甲基)。尽管有人建议使用羟甲基作为糖形成的基石,但它是一种反应性物质,直到最近才被发现。在这里,我们证明甲醛与它的异构体羟甲基反应生成乙醇醛,几乎可以无障碍地进行反应。这种羰基-烯型转化在低温和类似于地球外环境或星际云中发现的低温下,在没有碱和溶剂的情况下进行。正如我们通过三糖甘油醛的形成所证明的那样,羟甲基是迭代糖合成的基础。不会形成热力学上优选的酮糖二羟基丙酮,并且不可能在此处介绍的迭代合成中形成更多的支链糖。因此,结果提供了在非水条件下众所周知的蔗糖(Butlerow)反应与糖形成之间的联系。

更新日期:2018-09-11
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