2L-(2,3/4,5)-2,3,4-tri-O-benzyl-5-C-benzyloxymethyl-2,3,4,5-tetrahydroxycyclohexanone | 306968-48-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2L-(2,3/4,5)-2,3,4-tri-O-benzyl-5-C-benzyloxymethyl-2,3,4,5-tetrahydroxycyclohexanone
• 英文别名: (2S,3S,4S,5S)-2,3,4-tris(benzyloxy)-5-((benzyloxy)-methyl)-5-hydroxycyclohexan-1-one；2,3,4,7-tetra-O-benzyl-2-epi-valiolone；(2S,3S,4S,5S)-5-Hydroxy-2,3,4-tris(phenylmethoxy)-5-[(phenylmethoxy)methyl]-cyclohexanone；(2S,3S,4S,5S)-5-hydroxy-2,3,4-tris(phenylmethoxy)-5-(phenylmethoxymethyl)cyclohexan-1-one
• CAS: 306968-48-9
• 化学式: C₃₅H₃₆O₆
• 分子量: 552.667
• InChiKey: JWXHKWBUBUUEFP-WDKGQIBQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  41
• 可旋转键数：
  13
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  74.2
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2L-(2,3/4,5)-2,3,4-tri-O-benzyl-5-C-benzyloxymethyl-2,3,4,5-tetrahydroxycyclohexanone 在 palladium 10% on activated carbon 、 氢气 作用下， 以 乙醇 、 水 为溶剂， 反应 2.0h， 以2.7 mg的产率得到伏格列波糖杂质9
  参考文献：
  名称：

  Evolutionary Divergence of Sedoheptulose 7-Phosphate Cyclases Leads to Several Distinct Cyclic Products

  摘要：

  Sedoheptulose 7-phosphate cyclases are enzymes that utilize the pentose phosphate pathway intermediate,. sedoheptulose 7-phosphate, to generate cyclic precursors of many bioactive natural products, such as the antidiabetic drug acarbose, the crop protectant validamycin, and the natural sunscreens mycosporine-like amino acids. These proteins are phylogenetically related to the dehydroquinate (DHQ) synthases from the shikimate pathway and are part of the more recently recognized superfamily of sugar phosphate cyclases, which includes DHQ synthases, aminoDHQ synthases, and 2-deoxy-scyllo-inosose synthases. Through genome mining and biochemical studies, we identified yet another subset of DHQS-like proteins in the actinomycete Actinosynnema mirum and the myxobacterium Stigmatella aurantiaca DW4/3-1. These enzymes catalyze the conversion of sedoheptulose 7-phosphate to 2-epi-valiolone, which is predicted to be an alternative precursor for aminocyclitol biosynthesis. Comparative bioinformatics and biochemical analyses of these proteins with 2-epi-5-epi-valiolone synthases (EEVS) and desmethyl-4-deoxygadusol synthases (DDGS) provided further insights into their genetic diversity, conserved amino acid sequences, and plausible catalytic mechanisms. The results further highlight the uniquely diverse DHQS-like sugar phosphate cyclases, which may provide new tools for chemoenzymatic, stereospecific synthesis of various cyclic molecules.

  DOI：

  10.1021/ja3041866
• 作为产物：
  描述：

  (2S,3S,4S,5S)-2,3,4-tri-O-benzyl-5-C-<(benzyloxy)methyl>-6,6-dichloro-1-oxo-2,3,4,5-cyclohexanetetrol 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 甲苯 为溶剂， 反应 2.0h， 以49%的产率得到2L-(2,3/4,5)-2,3,4-tri-O-benzyl-5-C-benzyloxymethyl-2,3,4,5-tetrahydroxycyclohexanone
  参考文献：
  名称：

  Evolutionary Divergence of Sedoheptulose 7-Phosphate Cyclases Leads to Several Distinct Cyclic Products

  摘要：

  Sedoheptulose 7-phosphate cyclases are enzymes that utilize the pentose phosphate pathway intermediate,. sedoheptulose 7-phosphate, to generate cyclic precursors of many bioactive natural products, such as the antidiabetic drug acarbose, the crop protectant validamycin, and the natural sunscreens mycosporine-like amino acids. These proteins are phylogenetically related to the dehydroquinate (DHQ) synthases from the shikimate pathway and are part of the more recently recognized superfamily of sugar phosphate cyclases, which includes DHQ synthases, aminoDHQ synthases, and 2-deoxy-scyllo-inosose synthases. Through genome mining and biochemical studies, we identified yet another subset of DHQS-like proteins in the actinomycete Actinosynnema mirum and the myxobacterium Stigmatella aurantiaca DW4/3-1. These enzymes catalyze the conversion of sedoheptulose 7-phosphate to 2-epi-valiolone, which is predicted to be an alternative precursor for aminocyclitol biosynthesis. Comparative bioinformatics and biochemical analyses of these proteins with 2-epi-5-epi-valiolone synthases (EEVS) and desmethyl-4-deoxygadusol synthases (DDGS) provided further insights into their genetic diversity, conserved amino acid sequences, and plausible catalytic mechanisms. The results further highlight the uniquely diverse DHQS-like sugar phosphate cyclases, which may provide new tools for chemoenzymatic, stereospecific synthesis of various cyclic molecules.

  DOI：

  10.1021/ja3041866

文献信息

• A Highly Efficient and Shortcut Synthesis of Cyclitol Derivatives via Spiro Sugar Ortho Esters
  作者：Hiro Ohtake、Xiao-Liu Li、Moto Shiro、Shiro Ikegami

  DOI：10.1016/s0040-4020(00)00621-9

  日期：2000.9

  lactones via spiro sugar ortho esters is described. The key steps are the novel enol ether formation from sugar ortho esters with AlMe3 and the efficient intramolecular aldol cyclization of alkyl enol ethers with ZnCl2 in THF/H2O. Firstly, the spiro sugar ortho esters 3a–c were prepared from the benzyl protected sugar lactones 1a–c and 2,2-dimethylpropanediol (2). These ortho esters were efficiently converted

  描述了经由螺糖原酸酯由糖内酯制备环糖醇衍生物。的关键步骤是从糖原酸酯的新颖烯醇醚地层与阿尔梅3和烷基烯醇醚与氯化锌的有效分子内醛醇环化2在THF H / 2 O.首先，螺糖原酸酯图3a - Ç是从制备苄基保护的糖内酯1a – c和2,2-二甲基丙二醇（2）。通过在CH 2 Cl 2中处理AlMe 3，这些原酸酯被有效地转化为烯醇醚5a – c。。该反应的起始步骤是伴随着甲基阴离子插入而进行的吡喃环裂解，第二步骤是由AlMe 3的路易斯酸度引起的二恶烷开环。生成的烷基烯醇醚用DMSO / Ac 2 O处理，并且形成的酮化合物通过ZnCl 2催化的Aldol在THF / H 2 O中环化而转化为碳糖9a - c。总产量9a，9b，基于内酯1a – c的9c和9c分别为64％，64％和54％。
• Synthesis of the Carba-Analogs of the α-Pyranose and β-Pyranose Forms of Sedoheptulose 7-Phosphate and Probing the Stereospecificity of Sedoheptulose 7-Phosphate Cyclases
  作者：Arash Samadi、Samuel Tanoeyadi、Takeshi Tsunoda、Philip J. Proteau、Taifo Mahmud

  DOI：10.1021/acs.biochem.4c00034

  日期：2024.5.21

  proposed for the stereospecificity of EEVS and EVS: (1) variation in aldol acceptor geometry during enzyme catalysis, and (2) preselection of the α-pyranose or β-pyranose forms of the substrate by the enzymes. Yet, there is no direct evidence to support or rule out either of these hypotheses. Here we report the synthesis of the carba-analogs of the α-pyranose and β-pyranose forms of SH7P and their

  景天庚酮糖 7-磷酸 （SH7P） 环化酶是糖磷酸环化酶的一个子集，已知可催化初级和次级代谢中许多生物合成途径的第一步。其中包括 2-epi-5-epi-valiolone 合酶 （EEVS） 和 2-epi-valiolone 合酶 （EVS），这两种密切相关的 SH7P 环化酶，分别催化 SH7P 转化为 2-epi-5-epi-valiolone 和 2-epi-valiolone。然而，这两种同源酶如何使用共同底物产生立体化学不同的产物尚不清楚。对于 EEVS 和 EVS 的立体特异性，已经提出了两个相互竞争的假设：（1） 酶催化过程中羟醛受体几何形状的变化，以及 （2） 酶对底物的 α-吡喃糖或 β-吡喃糖形式的预选。然而，没有直接的证据支持或排除这些假设中的任何一个。在这里，我们报道了 SH7P 的 α-吡喃糖和 β-吡喃糖形式的碳巴类似物的合成，以及它们在探测 ValA （来自吸湿链霉菌亚种的