2-(1,1-dimethyl-but-3-ynyloxy)-tetrahydro-pyran | 23950-66-5

• 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: 2-(1,1-dimethyl-but-3-ynyloxy)-tetrahydro-pyran
• 英文别名: 4-methyl-4-tetrahydropyranyloxypent-1-yne；2-(2-tetrahydro-2-pyranyloxy)-2-methyl-4-pentin；2-Methyl-pentin-4-2-ol-tetrahydropyranylether；2-[(2-Methyl-4-pentyn-2-yl)oxy]tetrahydro-2H-pyran；2-(2-methylpent-4-yn-2-yloxy)oxane
• CAS: 23950-66-5
• 化学式: C₁₁H₁₈O₂
• 分子量: 182.263
• InChiKey: SHSCBAQSBLYDQI-UHFFFAOYSA-N

物化性质

• 沸点：
  251.4±35.0 °C(Predicted)
• 密度：
  0.95±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(1,1-dimethyl-but-3-ynyloxy)-tetrahydro-pyran 在 吡啶 、 四氧化锇 、 dihydroquinidine 4-chlorobenzoate 、 偶氮二异丁腈 、 camphor-10-sulfonic acid 、 碘 、 叔丁基锂 、 三正丁基氢锡 、 sodium hydrogensulfite 作用下， 以 甲醇 为溶剂， 反应 30.5h， 生成 (20R,22R,23R)-6β-methoxy-3α,5-cyclo-5α-cholestane-20,22,23,25-tetraol
  参考文献：
  名称：

  新型动物蜕皮甾体Gerardiasterone的合成与结构解析

  摘要：

  在DHQ-CLB作为手性配体的情况下，采用E-烯烃34的不对称二羟基化，以非对映选择性的方式实现了新的动物蜕皮类甾醇gerardiasterone的首次合成。该合成确认明确的gerardiasterone结构为（20 - [R，22 - [R，23小号）-2 β，3 β，14 α，20,22,23,25-heptahydroxy-5 β -cholest -7-烯-6-一（2a）。

  DOI：

  10.1016/0040-4020(96)00897-6
• 作为产物：
  描述：

  3,4-二氢-2H-吡喃 、 2-甲基-4-戊炔-2-醇 在 对甲苯磺酸 作用下， 以 二氯甲烷 为溶剂， 以85%的产率得到2-(1,1-dimethyl-but-3-ynyloxy)-tetrahydro-pyran
  参考文献：
  名称：

  新型蜕皮甾醇Gerardiasterone的合成与结构解析

  摘要：

  通过将E-烯烃22的非对映选择性二羟基化作为关键步骤，通过合成其新蜕皮类固醇Gerardiasterone的结构为2a。

  DOI：

  10.1016/s0040-4039(00)61409-0

文献信息

• Synthesis and Stereochemistry of Insect Derived Spiroacetals with Branched Carbon Skeletons
  作者：Yong Q. Tu、Achim Hübener、Hesheng Zhang、Christopher J. Moore、Mary T. Fletcher、Patricia Hayes、Konrad Dettner、Wittko Francke、Christopher S. P. McErlean、William Kitching

  DOI：10.1055/s-2000-8232

  日期：——

  7-dioxoaspiro[5.5]undecane system and are certain stereoisomers of the 2,4,8-trimethyl derivative, from the aposematic shield bug, Cantao parentum (White), and a 2,2,8-trimethyl derivative from the rove beetle, Ontholestes murinus (L.). The 1,6-dioxaspiro[4.5]decane system is represented by a stereoisomer of the 2,3,7-trimethyl derivative in the Cantao species. The elucidation of their structures and stereochemistry

  大约三十种结构不同的螺缩醛已从昆虫中表征，但只有三种具有分支的碳骨架。两种基于 1,7-二氧杂螺[5.5]十一烷系统，是 2,4,8-三甲基衍生物的某些立体异构体，来自 aposematic shield bug, Cantao parentum (White)，以及 2,2,8-来自流浪甲虫 Ontholestes murinus (L.) 的三甲基衍生物。1,6-二氧杂螺[4.5]癸烷系统由Cantao物种中的2,3,7-三甲基衍生物的立体异构体表示。描述了通过光谱、合成和对映选择性气相色谱对它们的结构和立体化学的阐明。
• A Highly Efficient Access to Spiroketals, Mono-unsaturated Spiroketals, and Furans: Hg(II)-Catalyzed Cyclization of Alkyne Diols and Triols
  作者：Kontham Ravindar、Maddi Sridhar Reddy、Pierre Deslongchamps

  DOI：10.1021/ol201102x

  日期：2011.6.17

  Hg(II) salts are identified as highly efficient catalysts for the versatile construction of spiroketals from alkyne diols in aqueous conditions. Monounsaturated spiroketals and furans were accessed with equal ease when propargylic triols (or propargylic diols) were subjected to similar conditions. Even the semiprotected alkyne diols gave the corresponding spiroketals with the same ease in a cascade manner. The reactions are Instant and high yielding at ambient temperatures. Regioselectivity issues are well addressed.
• Synthesis and absolute stereochemistry of spiroacetals in rove beetles (Coleoptera: Staphylinidae)
  作者：Hesheng Zhang、Mary T. Fletcher、Konrad Dettner、Wittko Francke、William Kitching

  DOI：10.1016/s0040-4039(99)01612-3

  日期：1999.10

  The unusual branched-carbon chain spiroacetal, 2,2,8-trimethyl-1,7-dioxaspiro[5.5]undecane, has been synthesised as its racemate and (6S,8R)-isomer. The natural compound, identified in the rove beetle, Ontholestes murinus (L.) proved to be the (6R,8S)-isomer. (E,E)-2,8-Dimethyl-1,7-dioxaspiro[5.5]undecane, a major component of the volatiles from the same insect, is the (2S,6R,8S)-isomer, but is largely racemic in Ontholestes tesselatus (Geoffr. Fourcr.). (C) 1999 Elsevier Science Ltd. All rights reserved.
• Synthesis of the Antiproliferative Agent Hippuristanol and Its Analogues via Suárez Cyclizations and Hg(II)-Catalyzed Spiroketalizations
  作者：Kontham Ravindar、Maddi Sridhar Reddy、Lisa Lindqvist、Jerry Pelletier、Pierre Deslongchamps

  DOI：10.1021/jo102054r

  日期：2011.3.4

  A full account of the synthesis of hippuristanol and its analogues is described. Hecogenin acetate was identified as a suitable and economical starting material for this work, and substrate-controlled stereo-selection was obtained throughout the construction of the key spiroketal unit. Suarez cyclization was first used, but Hg(II)-catalyzed spiroketalization of the 3-alkyne-1,7-diol motif was finally identified as the most convenient strategy.
• Olsson,L.-I. et al., Acta chemica Scandinavica. Series B: Organic chemistry and biochemistry, 1974, vol. 28, p. 765 - 770
  作者：Olsson,L.-I. et al.

  DOI：——

  日期：——