1,2:4,5-di-O-isopropylidene-D-arabinitol | 73543-86-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,2:4,5-di-O-isopropylidene-D-arabinitol
• 英文别名: 1,2:4,5-Di-O-isopropyliden-D-arabitol；1,2,5,6-Di-O-isopropyliden-D-mannit；bis[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]methanol
• CAS: 73543-86-9
• 化学式: C₁₁H₂₀O₅
• 分子量: 232.277
• InChiKey: NQJMKBQMFSCMFO-HTQZYQBOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  57.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1,2:4,5-di-O-isopropylidene-D-arabinitol 在 重铬酸吡啶 、 乙酸酐 作用下， 以 二氯甲烷 为溶剂， 生成
  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：

  3-O-formyl-1,2:4,5-di-O-isopropylidene-D-arabinitol 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以75%的产率得到1,2:4,5-di-O-isopropylidene-D-arabinitol
  参考文献：
  名称：

  碳水化合物异头烷氧基的还原性断裂。具有作为手性合成子的潜在用途的醛糖醇的合成。

  摘要：

  合成了一系列呋喃糖和吡喃糖形式的碳水化合物的异头硝酸酯和N-邻苯二甲酰亚胺基糖苷，以生成相应的烷氧基，并研究还原条件下的C1-C2片段化反应。该反应构成了将碳水化合物转化为碳较少的相应糖醇的两步法。使用这种方法，已经制备了具有D-赤藓糖醇，D-苏糖醇，D-木糖醇和D-阿拉伯糖醇立体化学的天然产物合成的有趣的四碳和五碳构件。1,2-O-异亚丙基-β-L-苏糖（40）和1-乙酰氨基-2,4,5-三-O-乙酰基-D-阿拉伯糖醇（50）的合成也已从1,2实现：5,6-二-O-异亚丙基-β-D-呋喃葡萄糖和2-乙酰氨基-3,4,6-三-O-乙酰基-2-脱氧-D-吡喃葡萄糖，

  DOI：

  10.1021/jo0156565

文献信息

• Regio- and stereoselective cyclizations of dianhydro sugar alcohols catalyzed by a chiral (salen)CoIII complex
  作者：Toshifumi Satoh、Tomoko Imai、Satoshi Umeda、Katsuyuki Tsuda、Hisaho Hashimoto、Toyoji Kakuchi

  DOI：10.1016/j.carres.2005.09.003

  日期：2005.12

  4-di- O -methyl- l -iditol ( 7 ), respectively. The cyclization of 3 and 5 is a novel method for obtaining 1,6-anhydro-3,4-di- O -methyl- d -mannitol ( 11 ) and a stereoselective route to 1,5-anhydro-3- O -methyl- l -arabinitol ( 13 ). It is proposed that the reaction occurs via endo -selective cyclization of an epoxy alcohol produced by the endo -selective ring-opening of one of the two epoxide moieties

  摘要（salen）Co III OAc（（R，R）-1和（S，S）-1）催化手性二脱水糖1,2：5,6-dianhydro-3,4-di-O的环化反应-甲基-d-葡萄糖醇（2），1,2：5,6-双脱水-3,4-二-O-甲基-d-甘露糖醇（3），1,2：5,6-双脱水-3,4 -二-O-甲基-1-ID醇（4）和1,2：4,5-二脱水-3-O-甲基-1-阿拉伯糖醇（5）是合成脱水醛糖醇的简便方法。使用（R，R）-1和（S，S）-1的2环化非对映选择性地形成2,5-脱水-3,4-二-O-甲基-d-甘露醇（6）和2,5-分别为脱水的3，4-二-O-甲基-1-ID-醇（7）。3和5的环化是获得1,6-脱水-3,4-二-O-甲基-d-甘露糖醇（11）的新方法和对1,5-脱水3-O-甲基的立体选择路线-l-阿拉伯糖醇（13）。
• Synthesis and radical fragmentation of carbohydrate anomeric nitrates. Formation of convenient chiral synthetic intermediates
  作者：Cosme G. Francisco、Elisa I. León、Pilar Moreno、Ernesto Suárez

  DOI：10.1016/s0957-4166(98)00326-7

  日期：1998.9

  A new procedure for the C1–C2 fragmentation of cyclic carbohydrates, through the formation of anomeric alkoxy radicals from the corresponding nitrate esters, with nBu3SnH/azobisisobutyronitrile (AIBN), affords acyclic alditols in good yields.

  通过与n Bu 3 SnH /偶氮二异丁腈（AIBN）由相应的硝酸酯形成异头烷氧基，形成一种环状糖类C1-C2裂解的新方法，可得到高产率的无环醛糖醇。
• ASYMMETRIC SYNTHESIS CATALYZED BY TRANSITION METAL COMPLEXES WITH CYCLIC CHIRAL PHOSPHINE LIGANDS
  申请人：THE PENN STATE RESEARCH FOUNDATION

  公开号：EP0918781B1

  公开（公告）日：2004-02-18
• Synthesis of Carbohydrates in Mineral-Guided Prebiotic Cycles
  作者：Hyo-Joong Kim、Alonso Ricardo、Heshan I. Illangkoon、Myong Jung Kim、Matthew A. Carrigan、Fabianne Frye、Steven A. Benner

  DOI：10.1021/ja201769f

  日期：2011.6.22

  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.
• Reductive Fragmentation of Carbohydrate Anomeric Alkoxy Radicals. Synthesis of Alditols with Potential Utility as Chiral Synthons
  作者：Cosme G. Francisco、Elisa I. León、Angeles Martín、Pilar Moreno、María S. Rodríguez、Ernesto Suárez

  DOI：10.1021/jo0156565

  日期：2001.10.1

  A series of anomeric nitrate esters and N-phthalimido glycosides of carbohydrates in furanose and pyranose forms have been synthesized in order to generate the corresponding alkoxy radicals and study the C1-C2 fragmentation reaction under reductive conditions. This reaction constitutes a two-step method for the transformation of carbohydrates into the corresponding alditols with one less carbon. Using

  合成了一系列呋喃糖和吡喃糖形式的碳水化合物的异头硝酸酯和N-邻苯二甲酰亚胺基糖苷，以生成相应的烷氧基，并研究还原条件下的C1-C2片段化反应。该反应构成了将碳水化合物转化为碳较少的相应糖醇的两步法。使用这种方法，已经制备了具有D-赤藓糖醇，D-苏糖醇，D-木糖醇和D-阿拉伯糖醇立体化学的天然产物合成的有趣的四碳和五碳构件。1,2-O-异亚丙基-β-L-苏糖（40）和1-乙酰氨基-2,4,5-三-O-乙酰基-D-阿拉伯糖醇（50）的合成也已从1,2实现：5,6-二-O-异亚丙基-β-D-呋喃葡萄糖和2-乙酰氨基-3,4,6-三-O-乙酰基-2-脱氧-D-吡喃葡萄糖，