1-(3',4',6'-tri-O-benzyl-α-D-mannopyranosyl)prop-2-ene | 767340-70-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-(3',4',6'-tri-O-benzyl-α-D-mannopyranosyl)prop-2-ene
• 英文别名: 3-C-(3,4,6-tri-O-benzyl-α-D-mannopyranosyl)1-propene；(2R,3R,4R,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-2-prop-2-enyloxan-3-ol
• CAS: 767340-70-5
• 化学式: C₃₀H₃₄O₅
• 分子量: 474.597
• InChiKey: UYWKXHISDGPRTR-XZTOTZIXSA-N

物化性质

• 沸点：
  607.9±55.0 °C(predicted)
• 密度：
  1.16±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  35
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 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-(3',4',6'-tri-O-benzyl-α-D-mannopyranosyl)prop-2-ene 在 吡啶 、 臭氧 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 生成 2-C-(3,4,6-tri-O-benzyl-2-O-tosyl-α-D-mannopyranosyl)acetaldehyde
  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
• 作为产物：
  描述：

  3,4,6-tri-O-acetyl-1,2-O-(1-methoxyethylidene)-β-D-mannopyranose 在 咪唑 、 三氟甲磺酸三甲基硅酯 、 2,6-二叔丁基-4-甲基苯酚 、 4 A molecular sieve 、 sodium hydride 、 potassium carbonate 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 67.0h， 生成 1-(3',4',6'-tri-O-benzyl-α-D-mannopyranosyl)prop-2-ene
  参考文献：
  名称：

  烯丙基-的立体选择性合成Ç -mannosyl化合物：临时硅连接分子内烯丙基化策略与烯丙基硅烷的使用

  摘要：

  在9个步骤中，由d-甘露糖合成了在C（2）处含有烯丙基二甲基甲硅烷基醚的甲基甘露糖苷16。与将TMSOTf反应在MeCN在室温进行Ç -glycosylation以提供α烯丙基Ç -mannosyl产品18具有优异的立体选择性。在一系列反应浓度范围内的交叉实验证明，反应是通过分子间途径进行的，而不是通过分子内传递途径进行的。在存在除酸剂2,6-DTBMP的情况下，这种烯丙基化反应具有极高的立体选择性，这可归因于烯丙基甲硅烷基醚16表现为烯丙基化剂。七元环过渡态的几何约束解释了分子内烯丙基转移的缺乏。将改性的烯丙基硅烷29a - c连接到甲基甘露糖苷15的C（2）OH上可以改善物质。系留甘露糖苷27a - c的反应在室温下，在MeCN中存在2,6-DTBMP的条件下，使用TMSOTf提供的产物范围取决于甲硅烷基醚系链上烷基取代基的大小。不论甲硅烷基醚系链上烷基取代基的大小如何，二烯产物都是主

  DOI：

  10.1021/jo049061w

文献信息

• 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。
• 1,5-Hydrogen Atom Transfer/Surzur–Tanner Rearrangement: A Radical Cascade Approach for the Synthesis of 1,6-Dioxaspiro[4.5]decane and 6,8-Dioxabicyclo[3.2.1]octane Scaffolds in Carbohydrate Systems
  作者：Elisa I. León、Ángeles Martín、Adrián S. Montes、Inés Pérez-Martín、María del Sol Rodríguez、Ernesto Suárez

  DOI：10.1021/acs.joc.1c01376

  日期：2021.11.5

  alkoxyl radicals were generated by the reaction of the corresponding N-alkoxyphthalimides with group 14 hydrides [n-Bu3SnH(D) and (TMS)3SiH], and in comparative terms, the reaction was also initiated by visible light photocatalysis using the Hantzsch ester/fac-Ir(ppy)3 procedure. Special attention was devoted to the influence of the relative stereochemistry of the centers involved in the radical sequence

  已经在一系列具有 3 -C- ( α, β- d , l - 吡喃葡萄糖基）1-丙醇和C -（α- d , l -吡喃葡萄糖基）甲醇结构，由手性池d - 和l - 糖制备。使用乙酰氧基和二苯氧基磷酸酯氧基作为离去基团可有效构建 10-deoxy-1,6-dioxaspiro[4.5]decane 和 4-deoxy-6,8-dioxabicyclo[3.2.1]octane 骨架。烷氧基自由基由相应的N反应生成-烷氧基邻苯二甲酰亚胺与第 14 族氢化物 [ n -Bu 3 SnH(D) 和 (TMS) 3 SiH]，比较而言，该反应也由使用 Hantzsch 酯/ fac -Ir(ppy) 3程序的可见光光催化引发. 特别关注自由基序列中涉及的中心的相对立体化学对反应结果的影响。将BF 3 •Et 2 O 作为催化剂添加到自由基序列中导致所需双环缩酮的产率显着增加。
• One-Pot Synthesis of 2-<i>C</i>-Branched Glycosyl Triazoles by Integrating 1,2-Cyclopropanated Sugar Ring-Opening Azidation and CuAAC Reaction
  作者：Zhongke Shen、Qin Tang、Wei Jiao、Huawu Shao、Xiaofeng Ma

  DOI：10.1021/acs.joc.2c02390

  日期：2022.12.16
• 1,2-Migration of 2‘-Oxoalkyl Group and Concomitant Synthesis of 2-<i>C</i>-Branched <i>O</i>-, <i>S</i>-Glycosides and Glycosyl Azides via 1,2-Cyclopropanated Sugars
  作者：Huawu Shao、Sanchai Ekthawatchai、Chien-Sheng Chen、Shih-Hsiung Wu、Wei Zou

  DOI：10.1021/jo0502854

  日期：2005.6.1

  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).
• Stereoselective Synthesis of Allyl-<i>C</i>-mannosyl Compounds:  Use of a Temporary Silicon Connection in Intramolecular Allylation Strategies with Allylsilanes
  作者：Julien Beignet、James Tiernan、Chang H. Woo、Benson M. Kariuki、Liam R. Cox

  DOI：10.1021/jo049061w

  日期：2004.9.1

  Methyl mannoside 16 containing an allyldimethylsilyl ether at C(2) was synthesized in nine steps from d-mannose. Reaction with TMSOTf in MeCN at room-temperature effected C-glycosylation to provide the α-allyl-C-mannosyl product 18 with excellent stereoselectivity. Crossover experiments over a range of reaction concentrations proved that reaction was proceeding via an intermolecular pathway rather

  在9个步骤中，由d-甘露糖合成了在C（2）处含有烯丙基二甲基甲硅烷基醚的甲基甘露糖苷16。与将TMSOTf反应在MeCN在室温进行Ç -glycosylation以提供α烯丙基Ç -mannosyl产品18具有优异的立体选择性。在一系列反应浓度范围内的交叉实验证明，反应是通过分子间途径进行的，而不是通过分子内传递途径进行的。在存在除酸剂2,6-DTBMP的情况下，这种烯丙基化反应具有极高的立体选择性，这可归因于烯丙基甲硅烷基醚16表现为烯丙基化剂。七元环过渡态的几何约束解释了分子内烯丙基转移的缺乏。将改性的烯丙基硅烷29a - c连接到甲基甘露糖苷15的C（2）OH上可以改善物质。系留甘露糖苷27a - c的反应在室温下，在MeCN中存在2,6-DTBMP的条件下，使用TMSOTf提供的产物范围取决于甲硅烷基醚系链上烷基取代基的大小。不论甲硅烷基醚系链上烷基取代基的大小如何，二烯产物都是主