3-(3,4,6-tri-O-benzyl-2-deoxy-α-D-glucopyranosyl)propene | 618387-37-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(3,4,6-tri-O-benzyl-2-deoxy-α-D-glucopyranosyl)propene
• 英文别名: (2R,3S,4R,6R)-6-allyl-3,4-bis(benzyloxy)-2-((benzyloxy)methyl)tetrahydro-2H-pyran；3-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)prop-1-ene；1-allyl-1,2-dideoxy-3,4,6-tri-O-benzyl-D-glucopyranose；(2R,3S,4R,6R)-3,4-bis(phenylmethoxy)-2-(phenylmethoxymethyl)-6-prop-2-enyloxane
• CAS: 618387-37-4
• 化学式: C₃₀H₃₄O₄
• 分子量: 458.598
• InChiKey: SJPLLCXSCOAHKE-CSBHBGLHSA-N

物化性质

• 沸点：
  570.8±50.0 °C(predicted)
• 密度：
  1.12±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  34
• 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：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-(3,4,6-tri-O-benzyl-2-deoxy-α-D-glucopyranosyl)propene 在 sodium methylate 、 臭氧 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成 2-(3,4,6-tri-O-benzyl-2-deoxy-β-D-glucopyranosyl)ethyl aldehyde
  参考文献：
  名称：

  通过烯醇化，β-消除和分子内环加成使2'-羰基烷基-C-糖苷发生差向异构。

  摘要：

  用4％NaOMe处理葡萄糖，半乳糖，甘露糖，2-脱氧和2-叠氮基糖的2'-羰基-α-C-糖吡喃糖苷导致端基异构体异构化，使其各自的β-端基异构体具有良好或优异的收率。α-C-吡喃半乳糖苷（10）的2'-醛在氘代甲醇中的差向异构化作用使β-端基异构体在1'-位具有唯一的氘代取代作用，排除了外糖参与的可能性中间体。当使用2,3-二-O-苄基-α/β-1C-阿拉伯呋喃糖苷的2'-醛（36）和2'-酮（41）作为底物时，我们能够获得各自的赤道α-C-阿拉伯吡喃糖苷（37和42）。这些观察结果证实，差向异构体涉及无环的α，β-不饱和醛或酮，它是由2'-羰基-α-C-糖苷的烯醇化和随后的β-消除形成的。此后发生分子内杂-迈克尔环加成反应，导致形成热力学控制的稳定产物，该产物仅是赤道的C-糖吡喃糖苷，但2'-羰基-C-呋喃糖苷除外，其中获得了两种端基异构体的混合物。

  DOI：

  10.1021/jo034446k
• 作为产物：
  描述：

  2-deoxy-3,4,6-tri-O-benzyl-D-glucono-1,5-lactone 、 烯丙基三丁基锡 在 chlorobis(cyclooctene)-iridium(I) dimer 、 二乙基硅烷 、 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 以42%的产率得到3-(3,4,6-tri-O-benzyl-2-deoxy-α-D-glucopyranosyl)propene
  参考文献：
  名称：

  铱催化的酯还原烯丙基化。

  摘要：

  描述了羧酸酯到α-支链醚的催化还原转化。该方法的重点是酯和内酯官能团的化学选择性铱催化的氢化硅烷化反应，得到甲硅烷基缩醛中间体。用路易斯酸处理后，这些半不稳定的中间体解离形成反应性氧碳鎓离子，烯丙基三丁基锡亲核试剂可以拦截这些离子，导致形成有价值的α-支链烷基-烷基醚衍生物。发现该还原性烯丙基化方法适用于一定范围的羧酸酯原料，并且证明了乙基相对于叔丁基酯具有良好的化学选择性。此外，α-氨基酸衍生产物的下游合成操作导致吡咯烷，哌啶和氮杂环庚烷骨架的有效形成。

  DOI：

  10.1021/acs.orglett.9b02119

文献信息

• <i>C</i>-Glycosylation enabled by <i>N</i>-(glycosyloxy)acetamides
  作者：Miao Liu、Bo-Han Li、Tian Li、Xia Wu、Meng Liu、De-Cai Xiong、Xin-Shan Ye

  DOI：10.1039/d0ob00561d

  日期：——

  The C-glycosylation of C-nucleophiles including allyltrimethylsilane, silyl enol ethers and phenols with N-(glycosyloxy)acetamides as glycosyl donors has been realized. This protocol provides a convenient and practical route for the synthesis of alkyl C-glycosides and aryl 2-deoxy-β-C-glycosides under mild reaction conditions.

  已经实现了包含N-（糖基氧基）乙酰胺作为糖基供体的C-亲核试剂（包括烯丙基三甲基硅烷，甲硅烷基烯醇醚和苯酚）的C-糖基化。该方案为在温和的反应条件下合成烷基C-糖苷和芳基2-脱氧-β-C-糖苷提供了方便实用的途径。
• Gold(<scp>i</scp>)-catalyzed C-glycosylation of glycosyl ortho-alkynylbenzoates: the role of the moisture sequestered by molecular sieves
  作者：Xiaoping Chen、Qiaoling Wang、Biao Yu

  DOI：10.1039/c6cc07218f

  日期：——

  C-Glycosylation of glycosyl ortho-hexynylbenzoates with allyltrimethylsilane or silyl enol ethers could proceed smoothly under the catalysis of Ph₃PAuNTf₂, wherein the moisture sequestered by the molecular sieves ensured the gold(i)-catalytic cycle.

  将glycosyl ortho-hexynylbenzoates与allyltrimethylsilane或硅烯醚进行C-糖基化反应，可在Ph3PAuNTf2的催化下顺利进行，其中分子筛吸附的水分确保了金（i）催化循环的进行。
• The Effect of Electrostatic Interactions on Conformational Equilibria of Multiply Substituted Tetrahydropyran Oxocarbenium Ions
  作者：Michael T. Yang、K. A. Woerpel

  DOI：10.1021/jo8017846

  日期：2009.1.16

  the conformational preference of the C-5 alkoxymethyl group. Although the monosubstituted C-5 alkoxymethyl substituent preferred a pseudoequatorial orientation, the C-5−C-6 bond rotation was controlled by an electrostatic effect. The preferred diaxial conformer of the trans-4,5-disubstituted tetrahydropyranyl system underscored the importance of electrostatic effects in dictating conformational equilibria

  通过对光谱、计算和反应性数据的分析，确定了与糖基阳离子相关的二氧碳鎓离子的三维结构。二氧碳鎓离子的假设低能量结构与实验确定的两者相关1H NMR 耦合常数和非对映选择性来自亲核取代反应。该方法证实了 C-3 烷氧基取代系统的假轴偏好，并揭示了 C-5 烷氧基甲基的构象偏好。尽管单取代的 C-5 烷氧基甲基取代基优选伪赤道取向，但 C-5-C-6 键旋转受静电效应控制。反式-4,5-二取代四氢吡喃系统的首选双轴构象异构体强调了静电效应在决定构象平衡方面的重要性。在 2-脱氧甘露糖体系中，虽然空间效应影响 C-5 烷氧基甲基取代基的取向，但由于静电稳定，全轴构象异构体受到青睐。
• Stereocontrolled Photocyclization of 1,2-Diketones: Application of a 1,3-Acetyl Group Transfer Methodology to Carbohydrates
  作者：Antonio J. Herrera、María Rondón、Ernesto Suárez

  DOI：10.1021/jo702663w

  日期：2008.5.1

  Photolysis of 1-glycosyl-2,3-butanodione derivatives using visible light is a mild and selective procedure for the synthesis of chiral 1-hydroxy-1-methyl-5-oxaspiro[3.5]nonan-2-one carbohydrate derivatives. The results strongly suggest that stereocontrol of the cyclization is dependent on conformational and stereoelectronic factors. Further oxidative opening, of the 1-hydroxy-1-methyl-2-cyclobutanone moiety affords new C-ketoside derivatives either in C- and O-glycoside series. This tandem two-step process could be considered to be a stereocontrolled 1,3-transference of an acetyl group, and it can be applied either to pyranose and furanose models.
• Erosion of Stereochemical Control with Increasing Nucleophilicity: <i>O</i>-Glycosylation at the Diffusion Limit
  作者：Matthew G. Beaver、K. A. Woerpel

  DOI：10.1021/jo902222a

  日期：2010.2.19

  Nucleophilic substitution reactions of 2-deoxyglycosyl donors indicated that the reactivity of the oxygen nucleophile has a significant impact on stereoselectivity. Employing ethanol as the nucleophile resulted in a 1:1 (alpha:beta) ratio of diastereomers under S(N)1-like reaction conditions. Stercoselective formation of the 2-deoxy-alpha-O-glycoside was only observed when weaker nucleophiles, such as trifluoroethanol, were employed. The lack of stercoselectivity observed in reactions of common oxygen nucleophiles can be attributed to reaction rates of the stereochemistry-determining step that approach the diffusion limit. In this scenario, both faces of the prochiral oxocarbenium ion are subject to nucleophilic addition to afford a statistical mixture of diastercomeric products. Control experiments confirmed that all nucleophilic substitution reactions were performed under kinetic control.