4,6-O-benzylidene-3-deoxy-D-glucal | 26532-06-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: 4,6-O-benzylidene-3-deoxy-D-glucal
• 英文别名: (4aR,8aS)-2-phenyl-4,4a,8,8a-tetrahydropyrano[3,2-d][1,3]dioxine
• CAS: 26532-06-9
• 化学式: C₁₃H₁₄O₃
• 分子量: 218.252
• InChiKey: ZWTPHMOGEFPPBJ-LAGVYOHYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4,6-O-benzylidene-3-deoxy-D-glucal 在 氯 作用下， 以 四氯化碳 为溶剂， 以89%的产率得到(4aR,6S,7S,8aS)-6,7-Dichloro-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxine
  参考文献：
  名称：

  D-葡糖衍生物氯化的一个新方面。4,6-O-亚苄基和取代基 atC-3 在 β-D-甘露糖和 β-D-阿拉伯异构体选择性形成中的重要作用

  摘要：

  与过乙酰基-和过苄基-D-glucal 中描述的先例报告相反，四氯化碳中 3-O-乙酰基-和 3-deoxy-4,6-O-benzylidene-D-glucal 的氯化主要发生在 β-侧分别给出β-D-甘露糖和β-D-阿拉伯加合物。

  DOI：

  10.1246/cl.1987.7
• 作为产物：
  描述：

  (2R,3S)-2-(hydroxymethyl)-3,6-dihydro-2H-pyran-3-ol 在 吡啶 、 mercury(II) diacetate 、 sodium hydride 作用下， 以 四氢呋喃 、 水 、 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 73.5h， 生成 4,6-O-benzylidene-3-deoxy-D-glucal
  参考文献：
  名称：

  1′,5′-Anhydro-l-ribo-hexitol Adenine Nucleic Acids (α-l-HNA-A): Synthesis and Chiral Selection Properties in the Mirror Image World

  摘要：

  The synthesis and a preliminary investigation of the base pairing properties of (6' -> 4']-linked 1',5'-anhydro-L-ribohexitol nucleic acids (alpha-L-HNA) have herein been reported through the study of a model oligoadenylate system in the mirror image world. Despite its considerable preorganization due to the rigidity of the "all equatorial" pyranyl sugar backbone, a-L-HNA represents a versatile informational biopolymer, in view of its capability to cross-communicate with natural and unnatural complements in both enantiomeric forms. This seems the result of an inherent flexibility of the oligonucleotide system, as witnessed by the singular formation of iso- and heterochiral associations composed of regular, enantiomorphic helical structures. The peculiar properties of alpha-L-HNA (and most generally of the alpha-HNA system) provide new elements in our understanding of the structural prerequisites ruling the stereoselectivity of the hybridization processes of nucleic acids.

  DOI：

  10.1021/acs.joc.5b00406

文献信息

• Sodium Borohydride-Nickel Chloride-Methanol Catalytic System for Regioselective Reduction of Electron-Rich Conjugated Dienes and Reductive Cleavage of Allyl Esters Involving π-Allylnickel Intermediates
  作者：Biao-Lin Yin、Cong-Bi Cai、Jin-Qiang Lai、Ze-Ren Zhang、Li Huang、Li-Wen Xu、Huan-Feng Jiang

  DOI：10.1002/adsc.201100612

  日期：2011.12

  The regioslective reduction of electron-rich dienes to monoolefins and the reductive cleavage of allyl esters were fulfilled by employing a sodium borohydride-nickel chloride-methanol catalytic system with exceedingly simple manipulations and high functional group tolerability. Both of the reductive reactions may involve π-allylnickel intermediates generated from fresh nickel boride.

  富电子二烯向单烯烃的区域反射还原和烯丙基酯的还原裂解是通过使用硼氢化钠-氯化镍-甲醇催化系统完成的，该系统操作极其简单，并且对官能团的耐受性极高。两种还原反应都可能涉及由新鲜的硼化镍产生的π-烯丙基镍中间体。
• High-pressure (2+2)cycloaddition of toluene-4-sulphonyl isocyanate to glycals
  作者：Marek Chmielewski、Zbigniew KaŁuża、Czesław Bełżecki、Piotr SaŁanski、Janusz Jurczak、Halina Adamowicz

  DOI：10.1016/s0040-4020(01)96639-6

  日期：1985.1

  High-pressure (2+2)cycloaddition of toluene-4-sulphonyl isocyanate to glycals is examined. Reactions proceed regiospecifically to afford single products in case of all 3-substituted glycals. Upon heating or even after standing at room temperature adducts undergo retro-addition to give starting glycals. Various aspects of the cycloaddition are discussed, especially ret-ro-reaction and rearrangement

  考察了异氰酸甲苯-4-磺酰基酯的高压（2 + 2）环加成反应。在所有3-取代的糖基的情况下，反应以区域特异性方式进行，得到单一产物。在加热时或什至在室温下放置后，加合物进行逆向添加以产生起始糖基。讨论了环加成反应的各个方面，特别是β-内酰胺的再反反应和重排为α，β-不饱和酰胺。
• [4 + 2] Cycloaddition reaction of dibenzyl azodicarboxylate and glycals
  作者：Yves Leblanc、Brian J. Fitzsimmons、James P. Springer、Joshua Rokach

  DOI：10.1021/ja00190a037

  日期：1989.4
• Selective deoxygenation of unsaturated carbohydrates with Pd(0)/Ph2SiH2/ZnCl2. Total synthesis of (+)-(S,S)-(6-methyltetrahydropyran-2-yl)acetic acid
  作者：Noam Greenspoon、Ehud Keinan

  DOI：10.1021/jo00251a011

  日期：1988.8
• KWOK, DAW-IONG;FARR, ROGER N.;DAVES, G. DOYLE (JR), J. ORG. CHEM., 56,(1991) N1, C. 3711-3713
  作者：KWOK, DAW-IONG、FARR, ROGER N.、DAVES, G. DOYLE (JR)

  DOI：——

  日期：——