methyl 4,6-O-benzylidene-2-deoxy-2-(2-propenyl)-α-D-allohexopyranoside | 126108-10-9

• 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: methyl 4,6-O-benzylidene-2-deoxy-2-(2-propenyl)-α-D-allohexopyranoside
• 英文别名: methyl 4,6-O-benzylidene-2-deoxy-2-C-propenyl-α-D-altropyranoside；methyl 4,6-O-benzylidene-2-deoxy-2-C-(prop-2-enyl)-α-D-altroside；(2R,4aR,6S,7S,8S,8aS)-6-methoxy-2-phenyl-7-prop-2-enyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-8-ol
• CAS: 126108-10-9
• 化学式: C₁₇H₂₂O₅
• 分子量: 306.359
• InChiKey: XCXMJWRFLIBIPB-OIBBZDHESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 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：

  methyl 4,6-O-benzylidene-2-deoxy-2-(2-propenyl)-α-D-allohexopyranoside 在 甲醇 、 重铬酸吡啶 、 硫酸 、 camphor-10-sulfonic acid 、 三氟化硼乙醚 、 氧气 、 二氯亚甲基二甲基氯化铵 、 三乙胺 、 copper dichloride 、 palladium dichloride 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 二氯甲烷 、 水 、 乙酸酐 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 生成 Toluene-4-sulfonic acid (2S,3R)-3-[(2R,3S,5R)-3-(bis-ethylsulfanyl-methyl)-5-methyl-6-oxo-tetrahydro-pyran-2-yl]-2-hydroxy-butyl ester
  参考文献：
  名称：

  Synthetic studies relating to the C1–C9 “Eastern” Half of Rosaramicin

  摘要：

  DOI：

  10.1016/s0040-4039(00)85204-1
• 作为产物：
  描述：

  methyl 2-O-benzyl-4,6-O-benzylidene-α-D-ribo-hexopyranosid-3-ulose 在 lithium aluminium tetrahydride 、 偶氮二异丁腈 作用下， 生成 methyl 4,6-O-benzylidene-2-deoxy-2-(2-propenyl)-α-D-allohexopyranoside
  参考文献：
  名称：

  Free radical substitutions of acyloxy groups in carbohydrate α-ketoesters

  摘要：

  当在回流苯中并在偶氮异丁腈（AIBN）作为自由基引发剂存在下用三正丁基氢化锡处理时，一系列含有α-酮酯官能团的碳水化合物衍生物会经历酰氧基的有效还原损失；在类似的条件下，但用烯丙基三正丁基锡代替氢化物，会发生有效的α-C-烯丙基化，轴向取代优先发生在酮酯位于构象稳定的吡喃环内的化合物中；该方法代表了碳水化合物衍生物脱氧和引入分支点的新方法。

  DOI：

  10.1039/c39910000690

文献信息

• The Synthesis of Some Carbohydrate-Derived Precursors to Tylonolide, the Aglycon of the Antibiotic Tylosin
  作者：AB Hughes、RV Stick、DMG Tilbrook

  DOI：10.1071/ch9901681

  日期：——

  Treatment of methyl 2,3-anhydro-4,6-O-benzylidene-α-D-alloside with the anion derived from trimethyl(prop-1-ynyl)silane, allylmagnesium chloride or isobutenylmagnesium chloride introduces a three- or four- carbon substituent at C2 of the sugar. In each case, a hydroboration-oxidation sequence helps convert the centre of unsaturation in the new substituent into a carboxylic acid residue. Subsequent manipulations allow the introduction ofanother carbon at C6 of the sugar to give a highly functionalized precursor to the C1-C9 fragment of tylonolide, the aglycon of the antibiotic tylosin. Attempts at the introduction of an axial methyl group at C4 of the extended sugar also described.

  将 2,3-脱水-4,6-O-亚苄基-α-D-阿洛糖甲基与三甲基（丙-1-炔基）硅烷、烯丙基氯化镁或异丁烯基氯化镁衍生的阴离子进行处理，可在糖的 C2 处引入三碳或四碳取代基。在每种情况下，氢硼氧化顺序都有助于将新取代基中的不饱和中心转化为羧酸残基。随后的操作允许在糖的 C6 处引入另一个碳，从而得到高度官能化的前体，形成泰诺内酯的 C1-C9 片段，即抗生素泰罗菌素的苷元。此外，还介绍了在扩展糖的 C4 处引入轴向甲基的尝试。
• Ligand exchange between cyanocuprates and allylic stannanes: a novel, direct route to allylic cuprates possessing remarkable reactivity and stability
  作者：Bruce H. Lipshutz、Robert Crow、Stuart H. Dimock、Edmund L. Ellsworth、Robin A. J. Smith、James R. Behling

  DOI：10.1021/ja00166a067

  日期：1990.5
• The Stereoselective Preparation of an Enantiomerically Pure Cyclopentane Using Intramolecular Aldol Cyclopentaannulation of a Glucose Derivative
  作者：Andrew J. Wood、David J. Holt、Maria-Consuelo Dominguez、Paul R. Jenkins

  DOI：10.1021/jo981225j

  日期：1998.11.1

  Methods for the annulation of carbohydrates have found extensive applications in organic synthesis. We report here a new protocol for the stereoselective conversion of glucose into an enantiomerically pure cyclopentane aldehyde 22. The readily available epoxide 15 was reacted with allyl Grignard to produce alcohol 16 in 86% yield. Swern oxidation followed by epimerization using triethylamine in N,N-dimethylformamide furnished the ketone 17 also in 86% yield. Regioselective deprotonation with lithium hexamethyldisilazane in THF was followed by methylation with methyl iodide and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidone as cosolvent to give 80% yield of ketone 18. Oxidation of ketone 18 by the Wacker procedure gave the 1,4-diketone 19 in 56% yield. Intramolecular aldol condensation occurred readily on treatment of diketone 19 with potassium tert-butoxide in toluene to furnish a 90% yield of enone 20. Treatment with N-bromosuccinimide produced the bromoester 21 in 72% yield, which was reduced to a mixture of aldehydes 22 (61%) and 23 (14%) with zinc shot in 2-propanol.
• Synthetic studies relating to the C1–C9 “Eastern” Half of Rosaramicin
  作者：Ustun Sunay、Bert Fraser-Reid

  DOI：10.1016/s0040-4039(00)85204-1

  日期：1986.1
• Free radical substitutions of acyloxy groups in carbohydrate α-ketoesters
  作者：Robert J. Ferrier、Cheang-Kuan Lee、Troy A. Wood

  DOI：10.1039/c39910000690

  日期：——

  A range of carbohydrate derivatives containing α-ketoester functionality undergo efficient reductive loss of the acyloxy groups when treated with tri-n-butyltin hydride in refluxing benzene and in the presence of azoisobutyronitrile (AIBN) as radical initiator; under similar conditions, but with allyltri-n-butyltin instead of the hydride, efficient α-C-allylation takes place with axial substitution occurring preferentially in compounds with the ketoesters located within conformationally stable pyranoid rings; the methods represent novel ways of deoxygenating carbohydrate derivatives and of introducing branch points.

  当在回流苯中并在偶氮异丁腈（AIBN）作为自由基引发剂存在下用三正丁基氢化锡处理时，一系列含有α-酮酯官能团的碳水化合物衍生物会经历酰氧基的有效还原损失；在类似的条件下，但用烯丙基三正丁基锡代替氢化物，会发生有效的α-C-烯丙基化，轴向取代优先发生在酮酯位于构象稳定的吡喃环内的化合物中；该方法代表了碳水化合物衍生物脱氧和引入分支点的新方法。