[(6S)-6-(phenylmethoxymethyl)oxan-2-yl] acetate | 1057657-69-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [(6S)-6-(phenylmethoxymethyl)oxan-2-yl] acetate
• CAS: 1057657-69-8
• 化学式: C₁₅H₂₀O₄
• 分子量: 264.321
• InChiKey: MFTFCWRAOZYAER-MLCCFXAWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [(6S)-6-(phenylmethoxymethyl)oxan-2-yl] acetate 在 叠氮基三甲基硅烷 、 四丁基二氟三苯硅酸铵 作用下， 以 二氯甲烷 为溶剂， 反应 0.16h， 生成 2-azide-6-benzyloxymethyltetrahydropyran
  参考文献：
  名称：

  THP衍生的吡啶鎓盐的制备及其与各种亲核试剂的反应

  摘要：

  已经开发了通过吡啶鎓型盐中间体进行的四氢吡喃基（THP）和相关的碳水化合物衍生的酯的异头位置的亲核取代。用TMSOTf（TMS =三甲基甲硅烷基）和2-取代的吡啶（例如2-对-甲苯基吡啶和2-甲氧基吡啶）处理6-取代的α-乙酰氧基-四氢吡喃可有效产生顺式py型盐。这些盐与各种亲核试剂（例如醇，叠氮化物和有机锌试剂）反应，形成亲核取代产物。这些过程的一个特征是它们发生在温和的条件下，并不影响对酸不稳定的保护基团。此外，使用叠氮化物和C-亲核试剂的反应生成具有高立体选择性的2,6-反式产物。

  DOI：

  10.1002/asia.201200234

文献信息

• 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。
• Solvent Effects in the Nucleophilic Substitutions of Tetrahydropyran Acetals Promoted by Trimethylsilyl Trifluoromethanesulfonate: Trichloroethylene as Solvent for Stereoselective <i>C</i>- and <i>O</i>-Glycosylations
  作者：Joanna C. Kendale、Elizabeth M. Valentín、K. A. Woerpel

  DOI：10.1021/ol501471c

  日期：2014.7.18

  The selectivities of nucleophilic substitution reactions of tetrahydropyran acetals promoted by trimethylsilyl trifluoromethanesulfonate depend upon the reaction solvent. Polar solvents favor the formation of SN1 products, while nonpolar solvents favor SN2 products. Trichloroethylene was identified as the solvent most likely to give SN2 products in both C- and O-glycosylation reactions.

  三氟甲磺酸三甲基甲硅烷基酯促进的四氢吡喃缩醛的亲核取代反应的选择性取决于反应溶剂。极性溶剂有利于S N 1 产物的形成，而非极性溶剂有利于S N 2 产物的形成。三氯乙烯被确定为最有可能在C-和O-糖基化反应中产生S N 2 产物的溶剂。
• 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.
• A Sequential Two‐Component Etherification/Oxa‐Conjugate Addition Reaction: Asymmetric Synthesis of (+)‐Leucascandrolide A Macrolactone
  作者：P. Andrew Evans、William J. Andrews

  DOI：10.1002/anie.200801357

  日期：2008.7.7