tert-butyl 5-hexynyl ether | 121587-75-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: tert-butyl 5-hexynyl ether
• 英文别名: 1-tert-butoxyhex-5-yne；6-tert-butoxyhex-1-yne；tBuO(CH2)4CCH；6-[(2-Methylpropan-2-yl)oxy]hex-1-yne
• CAS: 121587-75-5
• 化学式: C₁₀H₁₈O
• 分子量: 154.252
• InChiKey: JEIBMMJRSRQAGA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  tert-butyl 5-hexynyl ether 在 二异丁基氢化铝 、 碘 作用下， 以 正己烷 、 四氢呋喃 为溶剂， 反应 5.0h， 以93%的产率得到(E)-6-tert-butoxy-1-iodohex-1-ene
  参考文献：
  名称：

  Design and synthesis of bombykol analogues for probing pheromone-binding protein–ligand interactions

  摘要：

  Mono-, difluorinated, and thioanalogues of Bombyx mori female sex pheromones (bombykol, 1) were designed according to the ab initio calculations. These rationally designated analogues were synthesized using hydroboration and Sonogashira coupling strategy via (5E,7Z)-undecadien-1-ol (10) as a common intermediate. A new simplified binding assay based on nanoLC-linear ion trap ESI-MS for quantifying complexation of the B. mori pheromone-binding protein (BmPBP) with native (1) and prepared analogues was developed. The binding properties of native 1 and thioanalogue 4 with PBP were studied in detail. The dissociation constant (K-D) of 1 and 4 was determined to be 2.1 x 10(-6) M and 2.4 x 10(-6) M, respectively. The similar values for both ligands correlated with ab initio calculations. The new binding assay could be used to determine the K-D of other PBPs. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2008.10.106
• 作为产物：
  描述：

  5-己炔-1-醇 、 异丁烯 在 Amberlyst 作用下， 以 正己烷 为溶剂， 反应 14.0h， 以100%的产率得到tert-butyl 5-hexynyl ether
  参考文献：
  名称：

  Design and synthesis of bombykol analogues for probing pheromone-binding protein–ligand interactions

  摘要：

  Mono-, difluorinated, and thioanalogues of Bombyx mori female sex pheromones (bombykol, 1) were designed according to the ab initio calculations. These rationally designated analogues were synthesized using hydroboration and Sonogashira coupling strategy via (5E,7Z)-undecadien-1-ol (10) as a common intermediate. A new simplified binding assay based on nanoLC-linear ion trap ESI-MS for quantifying complexation of the B. mori pheromone-binding protein (BmPBP) with native (1) and prepared analogues was developed. The binding properties of native 1 and thioanalogue 4 with PBP were studied in detail. The dissociation constant (K-D) of 1 and 4 was determined to be 2.1 x 10(-6) M and 2.4 x 10(-6) M, respectively. The similar values for both ligands correlated with ab initio calculations. The new binding assay could be used to determine the K-D of other PBPs. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2008.10.106

文献信息

• Intramolecular conjugate addition reactions of amines and carbamates to 2,5-cyclohexadien-1-ones: Stereoselective synthesis of perhydroindoles
  作者：Douglas Bland、Gilles Chambournier、Vladimir Dragan、David J Hart

  DOI：10.1016/s0040-4020(99)00455-x

  日期：1999.7

  Intramolecular conjugate addition reactions of 4,4-disubstituted-2,5-cyclohexadien-1-ones are described within the context of possible approaches to manzamine A. Amine 4 provided tricycle 6, with improper relative stereochemistry for use in an approach to manzamine A. Carbamates 25 and 38 gave perhydroindoles 26 and 28b under conditions of thermodynamic control, respectively, with the proper relative

  在可能的甘露糖胺A方法的背景下描述了4,4-二取代-2,5-环己二烯-1-酮的分子内共轭加成反应。胺4提供了三轮车6，相对立体化学不适用于甘露糖胺A。氨基甲酸酯25和38在热力学控制条件下分别得到过氢吲哚26和28b，其中甘露糖胺A需要适当的相对立体化学；氨基甲酸酯25在热力学控制条件下得到非对映体过氢吲哚27。
• Synthesis of Quaternary Carbon Stereogenic Centers through Enantioselective Cu-Catalyzed Allylic Substitutions with Vinylaluminum Reagents
  作者：Fang Gao、Kevin P. McGrath、Yunmi Lee、Amir H. Hoveyda

  DOI：10.1021/ja106829k

  日期：2010.10.13

  efficiently (66-97% yield of isolated products) and in high site (>98% S(N)2')- and enantioselectivity [up to 99:1 enantiomer ratio (er)]. To the best of our knowledge, the present report puts forward the first cases of allylic substitution reactions that result in the generation of all-carbon quaternary stereogenic centers through the addition of a vinyl unit. The aryl- and vinyl-substituted vinylaluminum

  公开了催化对映选择性烯丙基取代 (EAS) 反应，其涉及使用烷基或芳基取代的乙烯基铝试剂并提供在其 C-3 位点含有季碳立体中心的 1,4-二烯。CC 键形成转化由 0.5-2.5 mol% 的带有手性双齿 N-杂环卡宾 (NHC) 配合物的磺酸盐促进，有效地提供所需的产物（66-97% 的分离产物产率）和高位点（>98 % S(N)2')- 和对映选择性 [高达 99:1 的对映异构体比 (er)]。据我们所知，本报告提出了烯丙基取代反应的第一个案例，该反应导致通过添加乙烯基单元产生全碳四元立体中心。芳基和乙烯基取代的乙烯基铝试剂，不能通过与二异丁基氢化铝直接反应高效制备，可以通过最近引入的相应末端炔烃与相同廉价金属氢化物的 Ni 催化反应获得。连续的 Ni 催化加氢金属化和 Cu 催化的 CC 键形成反应允许有效和选择性地合成一系列富含对映异构体的 EAS 产品，这些产品无法通过先前公
• Vicinal Diboronates in High Enantiomeric Purity through Tandem Site-Selective NHC−Cu-Catalyzed Boron−Copper Additions to Terminal Alkynes
  作者：Yunmi Lee、Hwanjong Jang、Amir H. Hoveyda

  DOI：10.1021/ja9089928

  日期：2009.12.30

  A Cu-catalyzed protocol for conversion of terminal alkynes to enantiomerically enriched diboronates is reported. In a single vessel, a site-selective hydroboration of an alkyne leads to the corresponding terminal vinylboronate, which undergoes a second site-selective and enantioselective hydroboration. Reactions proceed in the presence of 2 equiv of commercially available bis(pinacolato)diboron [B-2(pin)(2)] and 5-7.5 mol % loading of a chiral bidentate imidazolinium salt, affording diboronates in 60-93% yield and up to 97.5:2.5 enantiomeric ratio (er). The enantiomerically enriched products can be functionalized to afford an assortment of versatile organic molecules. Enynes are converted to unsaturated diboronates with high chemo- (>98% reaction of alkyne; <2% at alkene) and enantioselectivity (e.g., 94.5:5.5 er).
• Highly Site- and Enantioselective Cu-Catalyzed Allylic Alkylation Reactions with Easily Accessible Vinylaluminum Reagents
  作者：Yunmi Lee、Katsuhiro Akiyama、Dennis G. Gillingham、M. Kevin Brown、Amir H. Hoveyda

  DOI：10.1021/ja0782192

  日期：2008.1.1

  An efficient method for catalytic asymmetric allylic alkylation (AAA) of allylic phosphates with vinylaluminum reagents is reported. The vinylmetal reagents are prepared by reaction of commercially available DIBAL-H and a terminal alkyne. The resulting vinylaluminum reagent can be used directy, without isolation or purification. AAA reactions are promoted in the presence of 0.5-2.5 mol % of a readily available chiral N-heterocyclic carbene (NHC) complex and 1-5 mol % commercially available and air stable Cu salt (CUCl2-2H(2)O). The desired products are typically obtained within 2-12 h in 74% to 95% isolated yield, 77% to >98% ee, and in >98% E selectivity: >98% S(N)2' selectively is obtained in all but one instance (90%). The hydroalummation/catalytic AAA sequence can be performed in a single vessel, on gram scale.
• The hydroalumination of ω-terbutoxy alkynes an easy access to ω-hydroxy alkenyl iodides application to the synthesis of dienic insect pheromones
  作者：A. Alexakis、J.M. Duffault

  DOI：10.1016/s0040-4039(00)82315-1

  日期：1988.1