5-heptyn-1-yl tosylate | 70396-17-7

• 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: 5-heptyn-1-yl tosylate
• 英文别名: Heptin-5-ol-1-tosylat；hept-5-ynyl 4-methylbenzenesulfonate
• CAS: 70396-17-7
• 化学式: C₁₄H₁₈O₃S
• 分子量: 266.361
• InChiKey: AEZYKZAVEXYGMA-UHFFFAOYSA-N

物化性质

• 沸点：
  398.0±25.0 °C(Predicted)
• 密度：
  1.127±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.89
• 重原子数：
  18.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  5-heptyn-1-yl tosylate 在 三乙胺 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 (1,1-dimethylethyl)dimethyl<(1-phenyl-1(E)-octen-6-ynyl)oxy>silane
  参考文献：
  名称：

  Oxidative cyclization of .delta.,.epsilon.- and .epsilon.,.zeta.-unsaturated enol silyl ethers and unsaturated siloxycyclopropanes

  摘要：

  Oxidative cyclization of delta,epsilon- and epsilon,zeta-unsaturated enol silyl ethers 4a and 4b with cupric triflate and cuprous oxide or ceric ammonium nitrate and sodium bicarbonate in acetonitrile provides the tricyclic ketones 5a and 5b stereoselectively. These cyclizations proceed by oxidation of 4 to the cation radical 24 followed by cyclization of 24 to cation radical 27. This cation radical undergoes a second cyclization to give cation radical 30, which loses the silyl group, undergoes a second oxidation, and loses a proton to give 5. The stereochemistry of the cycloadduct is controlled by the stereochemistry of the enol ether. The Z-enol methyl ether (Z)-65 leads mainly to 5a while the E-enol methyl ether (E)-65 leads mainly to 6a. The oxidative cyclizations of 7, 13, 21, and 43 are also described. Oxidation of alpha-allyl silyl enol ethers 34a and 34b leads mainly to oxidation without cyclization to give the alpha,beta-unsaturated ketones 36a and 36b. Oxidative cyclizations of alkynyl silyl enol ethers 56 and 60 lead to 15 and 64, respectively. Oxidation of siloxycyclopropane 74 with Cu(BF4)2 generates cation radical 75, which cyclizes to 76, which is oxidized to give 21% of cyclopentane 77. This suggests that cation radicals are intermediates in the oxidative dimerization of siloxycyclopropanes.

  DOI：

  10.1021/jo00034a038
• 作为产物：
  描述：

  2-(hex-5-yn-1-yloxy)tetrahydro-2H-pyran 在 hydrolysis 作用下， 生成 5-heptyn-1-yl tosylate
  参考文献：
  名称：

  Oxidative cyclization of .delta.,.epsilon.- and .epsilon.,.zeta.-unsaturated enol silyl ethers and unsaturated siloxycyclopropanes

  摘要：

  Oxidative cyclization of delta,epsilon- and epsilon,zeta-unsaturated enol silyl ethers 4a and 4b with cupric triflate and cuprous oxide or ceric ammonium nitrate and sodium bicarbonate in acetonitrile provides the tricyclic ketones 5a and 5b stereoselectively. These cyclizations proceed by oxidation of 4 to the cation radical 24 followed by cyclization of 24 to cation radical 27. This cation radical undergoes a second cyclization to give cation radical 30, which loses the silyl group, undergoes a second oxidation, and loses a proton to give 5. The stereochemistry of the cycloadduct is controlled by the stereochemistry of the enol ether. The Z-enol methyl ether (Z)-65 leads mainly to 5a while the E-enol methyl ether (E)-65 leads mainly to 6a. The oxidative cyclizations of 7, 13, 21, and 43 are also described. Oxidation of alpha-allyl silyl enol ethers 34a and 34b leads mainly to oxidation without cyclization to give the alpha,beta-unsaturated ketones 36a and 36b. Oxidative cyclizations of alkynyl silyl enol ethers 56 and 60 lead to 15 and 64, respectively. Oxidation of siloxycyclopropane 74 with Cu(BF4)2 generates cation radical 75, which cyclizes to 76, which is oxidized to give 21% of cyclopentane 77. This suggests that cation radicals are intermediates in the oxidative dimerization of siloxycyclopropanes.

  DOI：

  10.1021/jo00034a038

文献信息

• Selectivity enhancement of epoxide hydrolase catalyzed resolution of 2,2-disubstituted oxiranes by substrate modification
  作者：Ingrid Osprian、Wolfgang Stampfer、Kurt Faber

  DOI：10.1039/b005203p

  日期：——

  A series of (±)-2,2-disubstituted oxiranes bearing an alkene or alkyne functional group were resolved by bacterial epoxide hydrolases with excellent selectivities. The presence of a carbon–carbon double or triple bond furnished a highly flexible system for substrate modification, which allowed the enantioselectivity to be tuned by rational substrate modification. Thus, a significant selectivity enhancement of more than a ten-fold increase of E-values was achieved by appropriate choice of the C–C multiple bond, i.e. by (i) choosing an alkene or alkyne moiety or by (ii) variation of the E/Z-configuration of olefinic substrates. The enantioenriched epoxides and vicinal diols thus obtained may be easily transformed into ω-functionalized building blocks containing a chiral fully substituted carbon atom by oxidative cleavage of the carbon–carbon multiple bond.

  一系列带有烯烃或炔烃官能团的(±)-2,2-二取代环氧化物通过细菌环氧化物水解酶得到了极佳的选择性拆分。碳-碳双键或三键的存在为底物修饰提供了一个高度灵活的系统，使得通过合理的底物修饰可以调节对映选择性。因此，通过适当选择C-C多重键，即通过（i）选择烯烃或炔烃部分或（ii）改变烯烃底物的E/Z构型，实现了E值超过十倍的显著选择性增强。由此获得的具有对映体富集的环氧化物和邻二醇可以通过碳-碳多重键的氧化断裂，容易地转化为含有手性完全取代碳原子的ω-官能化构建单元。
• Synthesis of Eight‐Membered Nitrogen Heterocycles via a Heterogeneous PtI ₂ ‐Catalyzed Cascade Cycloaddition Reaction of δ‐Aminoalkynes with Electron‐Deficient Alkynes
  作者：Xinhong Li、Songmeng Wang、Hongkai Wang、Weilin Wang、Lingyan Liu、Weixing Chang、Jing Li

  DOI：10.1002/adsc.201901644

  日期：2020.4.8

  cascade reaction of δ‐aminoalkynes was developed for the synthesis of various eight‐membered nitrogen heterocycles in excellent yields. The reaction proceeds via a hydration of δ‐aminoalkynes and subsequent intramolecular cyclization and intermolecular addition as well as ring‐expansion cascade reaction with another electron‐deficient alkynes. This method has the advantages of simple operation and mild

  开发了新颖的δ-氨基炔烃的异质PtI 2催化级联反应，用于以优异的产率合成各种八元氮杂环。该反应通过δ-氨基炔烃的水合，随后的分子内环化和分子间加成以及与另一种缺电子炔烃的扩环级联反应而进行。该方法操作简单，反应条件温和。而且，没有任何支持物的简单PtI 2可以通过简单的离心而容易地回收，而不会在1,2-二氯乙烷（DCE）中大量丧失活性。PtI 2的可回收性可归因于其在DCE中的不溶性。反应构成正式 [6 + 2]-环加法。
• Synthesis and cyclization reactions of alkynyl (.eta.5-cyclopentadienyltricarbonylmolybdenum and -tungsten) complexes
  作者：Patricia L. Watson、Robert G. Bergman

  DOI：10.1021/ja00502a020

  日期：1979.4
• A new route to functionalized trans-hydrindenones
  作者：Barry B. Snider、Thomas C. Kirk

  DOI：10.1021/ja00346a043

  日期：1983.4
• SNIDER, B. B.;KIRK, TH. C., J. AMER. CHEM. SOC., 1983, 105, N 8, 2364-2368
  作者：SNIDER, B. B.、KIRK, TH. C.

  DOI：——

  日期：——