methyl 3-O-benzoyl-4,6-O-benzylidene-α-D-arabino-hexapyranosid-2-ulose | 38993-01-0

• 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: methyl 3-O-benzoyl-4,6-O-benzylidene-α-D-arabino-hexapyranosid-2-ulose
• 英文别名: methyl 3-O-benzoyl-4,6-O-benzylidene-α-D-arabino-hexopyranosid-2-ulose；methyl 3-O-benzoyl-4,6-benzylidene-α-D-arabino-hexopyranosid-2-ulose；methyl 3-O-benzoyl-4,6-O-benzylidene-1-α-D-arabinopyranosid-2-ulose；methyl 3-o-benzoyl-4,6-o-benzylidene-α-D-arabino-hexopyranosidulose；[(4aR,6S,8S,8aR)-6-methoxy-7-oxo-2-phenyl-4,4a,8,8a-tetrahydropyrano[3,2-d][1,3]dioxin-8-yl] benzoate
• CAS: 38993-01-0
• 化学式: C₂₁H₂₀O₇
• 分子量: 384.386
• InChiKey: DZGBBXUQBPTOQM-IABNXAHASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  80.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 3-O-benzoyl-4,6-O-benzylidene-α-D-arabino-hexapyranosid-2-ulose 在 硼氘化钠 、 sodium methylate 作用下， 以 甲醇 、 水 为溶剂， 反应 16.0h， 生成 Methyl-α-D-<2-D₁>-glucopyranosid
  参考文献：
  名称：

  甲基4,6-O-亚苄基-2,3-二脱氧-2,3-二硝基-α-D-吡喃葡萄糖苷的制备及其选择性转化为相应的2-硝基-2-烯吡喃糖苷

  摘要：

  摘要在少量苯甲酸存在下，亚硝酸钠在苯水中用亚硝酸钠处理4,6-O-亚苄基-2,3-二脱氧-3-硝基-α-D-赤-己二-2-烯吡喃糖苷（3）作为相转移催化剂的三丁基十六烷基溴化phosph，以47％的收率得到2-硝基烯烃4。在1.3当量的存在下类似的反应。乙酸得到2，3-二硝基衍生物5，产率为58％。将其选择性地转化为2-硝基烯烃4。在这些反应中，亚硝酸根离子分别从3和4的轴向和赤道侧加成。

  DOI：

  10.1016/s0008-6215(00)85519-6
• 作为产物：
  描述：

  methyl 3-O-benzoyl-4,6-O-benzylidene-α-D-mannopyranoside 在 四丙基高钌酸铵 、 4 A molecular sieve 、 N-甲基吗啉氧化物 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以90%的产率得到methyl 3-O-benzoyl-4,6-O-benzylidene-α-D-arabino-hexapyranosid-2-ulose
  参考文献：
  名称：

  Chemistry of 1-Alkoxy-1-glycosyl Radicals:  The Manno- and Rhamnopyranosyl Series. Inversion of α- to β-Pyranosides and the Fragmentation of Anomeric Radicals

  摘要：

  The formation and stereoselective quenching of 1-mannopyranosyl radicals by a tributyltin hydride-mediated intramolecular 1,5-hydrogen abstraction sequence is described. A competing process is 1,4-hydrogen atom abstraction leading principally to glucopyran-2-ulosides. Fragmentation of the anomeric radical resulting in the formation of ring opened products is a problem in certain series. The chemistry is dictated to a considerable extent by the nature of the protecting groups employed with the 4,6-benzylidene series and, for rhamnose, the Ley 3,4-dispiroketal, being particularly susceptible to the 1,4-hydrogen atom abstraction but less to the fragmentation. Photochemical conditions are described, in which these side reactions are practically eliminated, and applied to the inversion of an alpha- to a beta-mannoside in a disaccharide.

  DOI：

  10.1021/jo951194h

文献信息

• Synthesis of 2,3-anhydro- and 3,4-anhydro-hexopyranosides having a methyl branch on the oxirane ring, and their reactions with some lithium methylcuprate reagents
  作者：Juji Yoshimura、Nobuya Kawauchi、Toshio Yasumori、Ken-ichi Sato、Hironobu Hashimoto

  DOI：10.1016/0008-6215(84)85203-9

  日期：1984.10

  synthesized. The reactions of these, together with those of a known 3-C-methyl epoxide (2), with three kinds of lithium methylcuprate were investigated. Except for 2 and 7, the vicinal monodeoxy di-C-methyl derivatives were obtained by attack of the cuprates at the sterically less-hindered site of the oxirane ring, irrespective of the stereoelectronic effect. Formation of a unique, acyclic 1-enitol derivative

  新增了三个具有2-C-甲基或3-C-甲基分支的2,3-脱水醛-吡喃二吡喃糖苷以及三个具有3-C-甲基（7）或4-C-甲基分支的3,4-脱水醛-吡喃二吡喃糖苷合成的。研究了它们与已知的3-C-甲基环氧化物（2）与三种甲基铜锂的反应。除2和7外，通过在环氧乙烷环的空间较少受阻的位点处的铜酸盐的攻击，获得邻位的单脱氧二-C-甲基衍生物，而与立体电子效应无关。确定了由2形成的独特的无环1-烯醇衍生物和由7形成的4-烯醇酮衍生物。还观察到了铜酸盐之间反应性的差异。
• TWO COMPLEMENTARY METHODS FOR INTRODUCTION OF<i>gem</i>-DIMETHYL GROUP IN HEXOPYRANOSIDE RING
  作者：Hironobu Hashimoto、Nobuya Kawauchi、Juji Yoshimura

  DOI：10.1246/cl.1985.965

  日期：1985.7.5

  Hexopyranosides having a gem-dimethyl group in the pyranose ring were synthesized By reductive cleavage of spiro-cyclopropane derivatives and By addition of methyl cuprates to methyl-branched enolone derivatives.

  通过螺环丙烷衍生物的还原裂解和甲基铜酸盐与甲基支链烯醇酮衍生物的加成，合成了在吡喃糖环中具有嵴二甲基基团的吡喃己糖苷。
• Total Synthesis of a Novel<i>β</i>-Glucosidase Inhibitor, Cyclophellitol Starting from D-Glucose
  作者：Ken-ichi Sato、Masayuki Bokura、Hironori Moriyama、Tetsutaro Igarashi

  DOI：10.1246/cl.1994.37

  日期：1994.1

  Cyclophellitol [1L-(1,2,4,6/3,5)-1,2-anhydro-6-(hydroxymethyl)-cyclohexane-1,2,3,4,5-pentol], a novel β-glucosidase inhibitor, has been synthesized from D-glucose via a branched-chain 6-deoxyhex-5-enopyranoside.

  Cyclophellitol [1L-(1,2,4,6/3,5)-1,2-anhydro-6-(hydroxymethyl)-cyclohexan-1,2,3,4,5-pentol]，一种新型β-葡萄糖苷酶抑制剂，已通过支链 6-deoxyhex-5-enopyranoside 从 D-葡萄糖合成。
• Preparation of methyl 4,6-O-benzylidene-2-deoxy-2-nitro-α-d-glucopyranoside from the corresponding 2-oximino derivative
  作者：Yoshifusa Tachimori、Tohru Sakakibara、Rokuro Sudoh

  DOI：10.1016/s0008-6215(00)85585-8

  日期：1981.9
• Methyl 2-O-acetyl-4-O-benzoyl-α-d-ribo-hexopyranosid-3-ulose
  作者：Vernon G.S. Box、Lynda L. Box、Earle V.E. Roberts

  DOI：10.1016/s0008-6215(00)88074-x

  日期：1982.4