1′-C-acetyl-3,4,6-tri-O-benzyl-1,2-cyclopropane-1,2-deoxy-α-D-glucopyranose | 857419-75-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1′-C-acetyl-3,4,6-tri-O-benzyl-1,2-cyclopropane-1,2-deoxy-α-D-glucopyranose
• 英文别名: 1-C-acetyl-3,4,6-tri-O-benzyl-1,2-cyclopropane-1,2-deoxy-α-D-glucopyranose；1-[(1S,3R,4S,5R,6S,7S)-4,5-bis(phenylmethoxy)-3-(phenylmethoxymethyl)-2-oxabicyclo[4.1.0]heptan-7-yl]ethanone
• CAS: 857419-75-1
• 化学式: C₃₀H₃₂O₅
• 分子量: 472.581
• InChiKey: ODHREFZJWDBUAD-URNDJICFSA-N

物化性质

• 沸点：
  604.8±55.0 °C(predicted)
• 密度：
  1.20±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  35
• 可旋转键数：
  11
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1′-C-acetyl-3,4,6-tri-O-benzyl-1,2-cyclopropane-1,2-deoxy-α-D-glucopyranose 在 bismuth(III) chloride 、 甲酸 、 硫酸 、 palladium 10% on activated carbon 、 氢气 、 烯丙基三甲基硅烷 作用下， 以 甲醇 、 甲苯 为溶剂， 生成
  参考文献：
  名称：

  由BiCl3促进的2,2-二取代的全氢呋喃[2,3-b]吡喃（和呋喃）衍生物的直接，高度非对映选择性合成。

  摘要：

  描述了一种合成2，2-二取代的全氢呋喃并[2,3-b]吡喃（和呋喃）衍生物的有效简便的方法。在BiCl3存在下，1,2-环丙烷化的糖与烯烃的环化反应具有非对映选择性。以良好至优异的产率获得了2，2-二取代的环化产物。

  DOI：

  10.1039/c3cc42292e
• 作为产物：
  描述：

  2-C-(3,4,6-tri-O-benzyl-2-O-tosyl-α-D-mannopyranosyl)acetaldehyde 在 potassium carbonate 、 pyridinium chlorochromate 作用下， 以 甲醇 为溶剂， 生成 1′-C-acetyl-3,4,6-tri-O-benzyl-1,2-cyclopropane-1,2-deoxy-α-D-glucopyranose
  参考文献：
  名称：

  1,2-Migration of 2‘-Oxoalkyl Group and Concomitant Synthesis of 2-C-Branched O-, S-Glycosides and Glycosyl Azides via 1,2-Cyclopropanated Sugars

  摘要：

  Treatment of 2'-oxoalkyl 2-O-Ms(Ts)-alpha-C-mannosides (4, 5, and 6) with base resulted in 1,2-cyclopropanation via an intramolecular S(N)2 reaction due to their 1,2-trans-diaxial configurations. The 1,2-cyclopropanated sugars (10 and 13) were reacted with various alcohols, thiols, and sodium azide to produce 2-C-branched O- and S-glycosides and glycosyl azides (11, 14-28) in good to excellent yields. In contrast, 1,2-cis 2'-oxoalkyl 2-O-Ms(Ts)-alpha-C-glucoside 9 formed an acyclic conjugated aldehyde (31) under basic conditions, which occurred by 1'-enolation followed by beta-elimination. An intramolecular Michael addition from 31 produced 2-O-Ms-beta-C-glucoside 30 as a major product. However, due to the electron-withdrawing effect exerted by 2-O-Ms compound 31 also undergoes a C2 epimerization to form 32. Thereafter, the intramolecular Michael addition led to the formation of both 1,2-trans 2'-oxoalkyl 2-O-Ms-alpha-C-mannoside 4 and its beta-anomer (33). Because beta-elimination/Michael addition and C2 epimerization are reversible reactions, equilibriums among 9, 31, 30, 32, 33, and 4 were established, which included the transformation of 1,2-cis C-glucoside 9 into 1,2-trans C-mannoside 4. The subsequent 1,2-cyclopropanation of 4 was an irreversible reaction yielding 1,2-cyclopropanated 10 and further conversion to 1,2-migration products (11 and 12).

  DOI：

  10.1021/jo0502854

文献信息

• 2-C<i>-</i>Branched Glycosides from 2‘-Carbonylalkyl 2-<i>O-</i>Ms(Ts)-<i>C-</i>Glycosides. A Tandem S_N2−S_N2 Reaction via 1,2-Cyclopropanated Sugars
  作者：Huawu Shao、Sanchai Ekthawatchai、Shih-Hsiung Wu、Wei Zou

  DOI：10.1021/ol0486627

  日期：2004.9.1

  [reaction: see text] Under basic conditions, 2'-aldehydo (acetonyl) 2-O-Ms(Ts)-alpha-C-glycosides undergo an intramolecular S(N)2 reaction to form 1,2-cyclopropanated sugars, which react with nucleophiles (alcohols, thiols, and azide) at the anomeric carbon to give 2-C-branched glycosides. By way of contrast, the 1,2-cyclopropanes derived from 2'-ketones only react with thiols to give 2-C-branched

  [反应：请参见文本]在基本条件下，2'-醛基（丙酮基）2-O-Ms（Ts）-α-C-糖苷会经历分子内S（N）2反应形成1,2-环丙烷化糖，在异头碳处与亲核试剂（醇，硫醇和叠氮化物）反应，生成2 C支链糖苷。相比之下，衍生自2'-酮的1,2-环丙烷仅与硫醇反应生成2-C-支链硫代糖苷。
• Stereoselective Synthesis of 2-<i>C</i>-Branched (Acetylmethyl) Oligosaccharides and Glycoconjugates: Lewis Acid-Catalyzed Glycosylation from 1,2-Cyclopropaneacetylated Sugars
  作者：Qiang Tian、Liang Dong、Xiaofeng Ma、Liyan Xu、Changwei Hu、Wei Zou、Huawu Shao

  DOI：10.1021/jo1016579

  日期：2011.2.18

  selectivity under both conditions. The stereoselectivities of glycosylation depend on the reactivity of donor sugars and Lewis acid catalyst, which effectively dictated the glycosylation pathways. The evidence suggests that galactosyl donors (e.g., 7) can undergo SN1 pathway with a strong Lewis acid (TMSOTf) and SN2 pathway under BF3·Et2O, whereas the glucosyl donors (e.g., 8 and 10) followed SN2 pathway.

  在路易斯酸存在下，作为糖基供体的1,2-环丙烷乙酰化的糖与一系列糖基受体（单糖，氨基酸和其他醇）反应，生成寡糖和含有2- C-乙酰甲基糖的糖缀合物。当使用TMSOTf作为催化剂时，半乳糖基供体具有良好的出色的α选择性，而当BF 3 ·Et 2 O被用作催化剂时，半乳糖基供体具有中等至良好的β选择性。然而，葡糖基供体在两种条件下均产生β-排他性选择性。糖基化的立体选择性取决于供体糖和路易斯酸催化剂的反应性，这有效地决定了糖基化途径。有证据表明，半乳糖基供体（例如7）可以经历小号Ñ 1个通路与强路易斯酸酯（TMSOTf）和S Ñ 2通路BF下3 ·的Et 2 O，而葡糖供体（例如，8和10），接着小号ñ 2途径。立体选择性也相应于通过2- C-乙酰甲基和糖基化中的异头碳鎓中间体形成的C2'-乙缩醛中间体的形成。
• Stereospecific [3+2] cycloaddition of 1,2-cyclopropanated sugars and ketones catalyzed by SnCl₄: an efficient synthesis of multi-substituted perhydrofuro[2,3-b]furans and perhydrofuro[2,3-b]pyrans
  作者：Xiaofeng Ma、Jichao Zhang、Qin Tang、Jun Ke、Wei Zou、Huawu Shao

  DOI：10.1039/c3cc48963a

  日期：——

  Stereospecific [3+2] cycloaddition of 1,2-cyclopropanated sugars and ketones catalyzed by SnCl4 is described. The method offers multi-substituted perhydrofuro[2,3-b]furans (bis-THFs) and perhydrofuro[2,3-b]pyrans containing a quaternary carbon chiral center in good to excellent yields.

  描述了SnCl4催化的1,2-环丙烷化糖和酮的立体特异性[3 + 2]环加成。该方法提供了具有季碳手性中心的多取代的全氢呋喃[2,3-b]呋喃（双-THF）和全氢呋喃[2,3-b]吡喃，产率高至优异。
• Zn(OTf)₂ promoted rearrangement of 1,2-cyclopropanated sugars with amines: a convenient method for the synthesis of 3-polyhydroxyalkyl-substituted pyrrole derivatives
  作者：Xudong Shen、Jianhui Xia、Peng Liang、Xiaofeng Ma、Wei Jiao、Huawu Shao

  DOI：10.1039/c5ob01620g

  日期：——

  A rearrangement reaction of 1,2-cyclopropanated sugars with amines promoted by Zn(OTf)₂ is described. The method offers 3-polyhydroxyalkyl-substituted pyrrole derivatives with multiple chiral centers.

  描述了由Zn(OTf)₂促进的1,2-环丙基糖与胺的重排反应。该方法提供了具有多个手性中心的3-多羟基烷基取代的吡咯衍生物。
• InCl₃ Catalyzed Highly Diastereoselective [3 + 2] Cycloaddition of 1,2-Cyclopropanated Sugars with Aldehydes: A Straightforward Synthesis of Persubstituted <i>Bis</i>-Tetrahydrofurans and Perhydrofuro[2,3-<i>b</i>]pyrans
  作者：Xiaofeng Ma、Qin Tang、Jun Ke、Xinglong Yang、Jichao Zhang、Huawu Shao

  DOI：10.1021/ol402192f

  日期：2013.10.18

  A mild and efficient strategy for the construction of persubstituted bis-tetrahydrofuran and perhydrofuro[2,3-b]pyran derivatives has been developed. Persubstituted cyclization products were obtained in good to excellent yields. The [3 + 2] cycloaddition of 1,2-cyclopropanated sugars with aldehydes in the presence of InCl3 is highly diastereoselective.

  已经开发了一种温和有效的策略来构建全取代的双-四氢呋喃和全氢呋喃[2,3- b ]吡喃衍生物。以良好至优异的产率获得全​​取代的环化产物。在InCl 3的存在下，1,2-环丙烷化糖与醛的[3 + 2]环加成反应具有非对映选择性。