(2S,3R)-2-prop-2-ynyloxan-3-ol

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (2S,3R)-2-prop-2-ynyloxan-3-ol
• 化学式: C₈H₁₂O₂
• 分子量: 140.182
• InChiKey: MHBWWPFAWWPSEH-SFYZADRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2S,3R)-2-prop-2-ynyloxan-3-ol 在 edetate disodium 、 potassium carbonate Sodium tetraborate decahydrate 、 正丁基锂 、 Oxone 、 Shi's ketone 、 四甲基乙二胺 、 三氟化硼乙醚 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 59.58h， 生成 (2R,3R,4aS,8aR)-2-trimethylsilanyl-2-(3-trimethylsilanylprop-2-ynyl)octahydropyrano[3,2-b]pyran-3-ol
  参考文献：
  名称：

  SiMe₃-Based Homologation−Epoxidation−Cyclization Strategy for Ladder THP Synthesis

  摘要：

  [GRAPHICS]A trimethylsilyl (SiMe3) group is the basis of a strategy that emulates the three fundamental proposed processes in ladder polyether biosynthesis: chain homologation, stereoselective epoxidation (>95% ee or >95:5 dr), and endo-selective, stereospecific (inversion) hydroxyepoxide cyclization (>95:5 endo:exo, >95% dr). A tris-THP was synthesized in 18 total operations from commercial materials using this approach.

  DOI：

  10.1021/ol0347040
• 作为产物：
  描述：

  2-Methoxy-2-(3-trimethylsilanyl-prop-2-ynyl)-tetrahydro-pyran-3-ol 在 三乙基硅烷 、 三氟甲磺酸三甲基硅酯 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 生成 (2S,3R)-2-prop-2-ynyloxan-3-ol
  参考文献：
  名称：

  A Reiterative Synthesis of Trans-Fused Polypyrans via Tungsten Pentacarbonyl-Promoted Alkynol Endocyclization

  摘要：

  Endocyclization of 1-alkyn-5-ols occurs in the presence of tungsten pentacarbonyl-THF complex to give cyclic six-membered tungsten oxacarbenes which are easily converted to alpha-stannyl enol ethers by treatment with Bu3SnOTf and Et3N. These stannylated dihydropyrans undergo organocuprate-mediated alkylation to provide 6-(2-propynyl)-3,4-dihydro-2H-pyrans. Oxidation of these propargylated dihydropyrans with m-CPBA followed by reduction with Et3SiH under Lewis acid conditions generates another trans-fused 1-alkyn-5-ol. Repetition of this process provides are iterative synthesis of trans-fused polypyrans.

  DOI：

  10.1021/jo980058k

文献信息

• New synthetic strategies for the stereocontrolled synthesis of substituted ‘skipped’ diepoxides
  作者：Christopher J. Morten、Timothy F. Jamison

  DOI：10.1016/j.tet.2009.05.074

  日期：2009.8

  This report describes a number of new synthetic approaches toward methyl-substituted mono- and diepoxy alcohols that serve as substrates for endo-selective epoxide-opening cascades. The key transformations involve the manipulation of alkynes. Highlighted are the directed methylmetalation of bishomopropargylic alcohols, the bromoallylation of alkynes, and Pd-catalyzed cross-coupling between an alkenyl

  这份报告描述了一些新的合成方法，用于甲基取代的单和双环氧醇作为内选择性环氧化物开放级联的底物。关键的转化涉及炔烃的操作。重点是双炔丙醇的定向甲基金属化、炔烃的溴烯丙基化以及 Pd 催化的烯基硼酸酯和烯丙基溴之间的交叉偶联。
• Tungsten carbonyl-induced cyclizations of alkynyl alcohols to dihydropyranylidene carbenes and α-stannyl dihydropyrans
  作者：Frank E. McDonald、Jason L. Bowman

  DOI：10.1016/0040-4039(96)00961-6

  日期：1996.7

  en pentacarbonyl induces cyclization to the corresponding tungsten dihydropyranylidene carbenes. These carbenes can be converted into α-stannyl dihydropyrans upon reaction with tributyltin triflate and triethylamine. This strategy provides the first general preparation of six-membered ring oxacarbenes of the group VI metals, and a novel synthesis of α-stannyl dihydropyrans from acyclic compounds.

  1-炔-5-醇与四氢呋喃-钨五羰基的反应诱导环化为相应的二氢吡喃基钨硬脂酸钨。在与三氟甲磺酸三丁基锡和三乙胺反应后，这些碳烯可以转化为α-锡烷基二氢吡喃。该策略提供了第VI族金属的六元环氧杂卡宾的第一个常规制备方法，以及从无环化合物合成α-锡烷基二氢吡喃的新方法。
• Morten, Christopher J.; Jamison, Timothy F., Journal of the American Chemical Society, 2009, vol. 131, p. 6678 - 6679
  作者：Morten, Christopher J.、Jamison, Timothy F.

  DOI：——

  日期：——
• SiMe₃-Based Homologation−Epoxidation−Cyclization Strategy for Ladder THP Synthesis
  作者：Timothy P. Heffron、Timothy F. Jamison

  DOI：10.1021/ol0347040

  日期：2003.6.1

  [GRAPHICS]A trimethylsilyl (SiMe3) group is the basis of a strategy that emulates the three fundamental proposed processes in ladder polyether biosynthesis: chain homologation, stereoselective epoxidation (>95% ee or >95:5 dr), and endo-selective, stereospecific (inversion) hydroxyepoxide cyclization (>95:5 endo:exo, >95% dr). A tris-THP was synthesized in 18 total operations from commercial materials using this approach.
• A Reiterative Synthesis of <i>Trans</i>-Fused Polypyrans via Tungsten Pentacarbonyl-Promoted Alkynol Endocyclization
  作者：Jason L. Bowman、Frank E. McDonald

  DOI：10.1021/jo980058k

  日期：1998.5.1

  Endocyclization of 1-alkyn-5-ols occurs in the presence of tungsten pentacarbonyl-THF complex to give cyclic six-membered tungsten oxacarbenes which are easily converted to alpha-stannyl enol ethers by treatment with Bu3SnOTf and Et3N. These stannylated dihydropyrans undergo organocuprate-mediated alkylation to provide 6-(2-propynyl)-3,4-dihydro-2H-pyrans. Oxidation of these propargylated dihydropyrans with m-CPBA followed by reduction with Et3SiH under Lewis acid conditions generates another trans-fused 1-alkyn-5-ol. Repetition of this process provides are iterative synthesis of trans-fused polypyrans.