2,4-bis(hydroxymethyl)-1,2,3,4,5-pentanepantaol | 65997-85-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,4-bis(hydroxymethyl)-1,2,3,4,5-pentanepantaol
• 英文别名: 2,4-di-C-(hydroxymethyl)pentitol；2,4-bis(hydroxymethyl)pentitol；2,4-bis-hydroxymethyl-pentane-1,2,3,4,5-pentaol；2,4-bis-hydroxymethyl-pentitol；(2,4-Bis(hydroxymethyl)-1,2,3,4,5-pentanpentol；2,4-Bis(hydroxymethyl)pentane-1,2,3,4,5-pentol
• CAS: 65997-85-5
• 化学式: C₇H₁₆O₇
• 分子量: 212.2
• InChiKey: KBDGHHUZXAJTDY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -4.7
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  142
• 氢给体数：
  7
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2,4-bis(hydroxymethyl)-1,2,3,4,5-pentanepantaol 、 乙酸酐 在 吡啶 、 4-二甲氨基吡啶 作用下， 反应 72.0h， 以95%的产率得到2,4-bis(acetoxymethyl)pentane-1,2,3,4,5-pentayl pentaacetate
  参考文献：
  名称：

  Synthesis of Carbohydrates in Mineral-Guided Prebiotic Cycles

  摘要：

  One present obstacle to the "RNA-first" model for the origin of life is an inability to generate reasonable "hands off" scenarios for the formation of carbohydrates under conditions where they might have survived for reasonable times once formed. Such scenarios would be especially compelling if they deliver pent(ul)oses, five-carbon sugars found in terran genetics, and exclude other carbohydrates (e.g., aldotetroses) that may also be able to function in genetic systems. Here, we provide detailed chemical analyses of carbohydrate premetabolisin, showing how borate, molybdate, and calcium minerals guide the formation of tetroses (C(4)H(8)O(4)), heptoses (C(7)H(14),O(7)), and pentoses (C(5)H(10)O(5)), including the ribose found in RNA, in "hands off" experiments, starting with formaldehyde and glycoaldehyde. These results show that pent(ul)oses would almost certainly have formed as stable borate complexes on the surface of an early Earth beneath a humid CO(2) atmosphere suffering electrical discharge. While aldotetroses form extremely stable complexes with borate, they are not accessible by pathways plausible under the most likely early Earth scenarios. The stabilization by borate is not, however, absolute. Over longer times, material is expected to have passed from borate-bound pent(ul)oses to a branched heptulose, which is susceptible to Cannizzaro reduction to give dead end products. We show how this fate might be avoided using molybdate-catalyzed rearrangement of a branched pentose that is central to borate-moderated cycles that fix carbon from formaldehyde. Our emerging understanding of the nature of the early Earth, including the presence of hydrated rocks undergoing subduction to form felsic magmas in the early Hadean eon, may have made borate and molydate species available to prebiotic chemistry, despite the overall "reduced" state of the planet.

  DOI：

  10.1021/ja201769f
• 作为产物：
  描述：

  1,2:4,5-di-O-isopropylidene-D-arabinitol 在 lithium aluminium tetrahydride 、 重铬酸吡啶 、 乙酸酐 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 6.0h， 生成 2,4-bis(hydroxymethyl)-1,2,3,4,5-pentanepantaol
  参考文献：
  名称：

  Synthesis of Carbohydrates in Mineral-Guided Prebiotic Cycles

  摘要：

  One present obstacle to the "RNA-first" model for the origin of life is an inability to generate reasonable "hands off" scenarios for the formation of carbohydrates under conditions where they might have survived for reasonable times once formed. Such scenarios would be especially compelling if they deliver pent(ul)oses, five-carbon sugars found in terran genetics, and exclude other carbohydrates (e.g., aldotetroses) that may also be able to function in genetic systems. Here, we provide detailed chemical analyses of carbohydrate premetabolisin, showing how borate, molybdate, and calcium minerals guide the formation of tetroses (C(4)H(8)O(4)), heptoses (C(7)H(14),O(7)), and pentoses (C(5)H(10)O(5)), including the ribose found in RNA, in "hands off" experiments, starting with formaldehyde and glycoaldehyde. These results show that pent(ul)oses would almost certainly have formed as stable borate complexes on the surface of an early Earth beneath a humid CO(2) atmosphere suffering electrical discharge. While aldotetroses form extremely stable complexes with borate, they are not accessible by pathways plausible under the most likely early Earth scenarios. The stabilization by borate is not, however, absolute. Over longer times, material is expected to have passed from borate-bound pent(ul)oses to a branched heptulose, which is susceptible to Cannizzaro reduction to give dead end products. We show how this fate might be avoided using molybdate-catalyzed rearrangement of a branched pentose that is central to borate-moderated cycles that fix carbon from formaldehyde. Our emerging understanding of the nature of the early Earth, including the presence of hydrated rocks undergoing subduction to form felsic magmas in the early Hadean eon, may have made borate and molydate species available to prebiotic chemistry, despite the overall "reduced" state of the planet.

  DOI：

  10.1021/ja201769f

文献信息

• Formose Reactions. XXVIII. Selective Formation of 2,4-Bis(hydroxymethyl)-3-pentulose in<i>N</i>,<i>N</i>-Dimethylformamide–Water Mixed Solvent
  作者：Yoshihiro Shigemasa、Takaaki Ueda、Hiroyuki Saimoto

  DOI：10.1246/bcsj.63.389

  日期：1990.2

  Dihydroxyacetone, DL-glycero-tetrulose, and 2,4-bis(hydroxymethyl)-3-pentulose (2,4-BH-3-P) were favorably formed in a formose reaction by choosing a suitable ratio of water to N,N-dimethylformamide used as solvent or a suitable [thiamine·HCl]/[HCHO] ratio. The formose reaction was strongly affected by the concentration of formaldehyde in the water layer. Under the reaction conditions studied, thiamine

  通过选择合适的水与 N,N 的比例，二羟基丙酮、DL-甘油四糖和 2,4-双(羟甲基)-3-戊酮糖 (2,4-BH-3-P) 在甲糖反应中有利地形成-二甲基甲酰胺用作溶剂或合适的[硫胺素·HCl]/[HCHO]比率。甲糖反应受水层中甲醛浓度的强烈影响。在研究的反应条件下，硫胺迅速分解。从反应混合物中分离出 2,4-BH-3-P，并通过 MS、IR 和 NMR 技术进行表征。还提出了形成 2,4-BH-3-P 的途径。
• Formose Reactions. XIV. A Selective Formose Reaction in the Presence of a Slight Amount of Calcium Ions
  作者：Yoshihiro Shigemasa、Tsuyoshi Taji、Eiichi Waki、Ruka Nakashima

  DOI：10.1246/bcsj.54.1403

  日期：1981.5

  important factor in obtaining the selective formation of the three-branched sugar alcohols. Under these reaction conditions, the α,β-enediol structure is required in an effective co-catalyst for the formose reaction. 2-(Hydroxymethyl)glycerol, 3-(hydroxymethyl)pentitol, and 2,4-bis(hydroxymethyl)pentitol were formed with a high selectivity in the formose reactions catalyzed by KOH, Mg(OH)2, Fe(OH)3

  发现在少量钙和 D-果糖存在下的甲糖反应产生三种产物，2-（羟甲基）甘油、3-（羟甲基）戊醇和 2,4-双（羟甲基）戊醇，具有高选择性。还讨论了影响选择性的各种因素：[Ca]、pH、[D-果糖]、反应温度、助催化剂和金属氢氧化物。相对于 [Ca] 的甲醛量是获得三支链糖醇选择性形成的最重要因素。在这些反应条件下，甲糖反应的有效助催化剂需要α,β-烯二醇结构。2-(羟甲基)甘油、3-(羟甲基)戊醇和2,4-双(羟甲基)戊醇在KOH、Mg(OH)2、Fe(OH)3催化的甲糖反应中以高选择性形成，和氢氧化锂。
• Selective Formation of 2-Hydroxy-3,3-bis(hydroxymethyl)-<b><i>γ</i></b>-butyrolactone from Formaldehyde on Hydrotalcite-Type Catalysts
  作者：Tadashi Mizutani、Yasushi Miki、Ruka Nakashima、Haruo Fujita、Hisanobu Ogoshi

  DOI：10.1246/bcsj.69.425

  日期：1996.2

  As a model for prebiotic sugar formation under neutral to acidic conditions, reactions of formaldehyde over hydrotalcite-type catalysts were investigated. Heating an aqueous solution of formaldehyde at 140—200 °C for 12 h over Ni–Fe hydrotalcite-type catalyst afforded 2-hydroxy-3,3-bis(hydroxymethyl)-γ-butyrolactone selectively, a 5.8% yield based on gas–liquid chromatographic analysis. The structure

  作为在中性至酸性条件下形成益生元糖的模型，研究了甲醛在水滑石型催化剂上的反应。在 Ni-Fe 水滑石型催化剂上将甲醛水溶液在 140-200 °C 下加热 12 小时，选择性地提供 2-羟基-3,3-双（羟甲基）-γ-丁内酯，基于气体的产率为 5.8%液相色谱分析。通过 1H 和 13C NMR 和 1H-13C HSQC、HMBC 和 13C-13C 2D INADEQUATE NMR 实验确定了结构。
• SHIGEMASA, YOSHIHIRO;UEDA, TAKAAKI;SAIMOTO, HIROYUKI, BULL. CHEM. SOC. JAP., 63,(1990) N, C. 389-394
  作者：SHIGEMASA, YOSHIHIRO、UEDA, TAKAAKI、SAIMOTO, HIROYUKI

  DOI：——

  日期：——
• Formose reactions. 5. A selective formose reaction
  作者：Yoshihiro Shigemasa、Osamu Nagae、Chikahiro Sakazawa、Ruka Nakashima、Teruo Matsuura

  DOI：10.1021/ja00472a056

  日期：1978.2