(4Z)-1,8-bis-(tetrahydropyran-2-yloxy)-oct-4-ene-2,6-diyne | 178382-93-9

• 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: (4Z)-1,8-bis-(tetrahydropyran-2-yloxy)-oct-4-ene-2,6-diyne
• 英文别名: 1,8-bis-(tetrahydropyran-2-yloxy)-oct-4-ene-2,6-diyne；1,8-bis(tetrahydropyran-2-yloxy)oct-4-ene-2,6-diyne；2-[(Z)-8-(oxan-2-yloxy)oct-4-en-2,6-diynoxy]oxane
• CAS: 178382-93-9
• 化学式: C₁₈H₂₄O₄
• 分子量: 304.386
• InChiKey: PSMCMNGKDCKXRM-UPHRSURJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4Z)-1,8-bis-(tetrahydropyran-2-yloxy)-oct-4-ene-2,6-diyne 在 氢氧化钾 、 溴 、 三苯基膦 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.25h， 生成 cis-1,8-bis(pyridin-3-oxy)oct-4-ene-2,6-diyne
  参考文献：
  名称：

  Metalloenediynes:  Ligand Field Control of Thermal Bergman Cyclization Reactions

  摘要：

  We report the preparation and thermal reactivities of unique Cu(I) and Cu(II) metalloenediyne complexes of the flexible 1,8-bis(pyridine-3-oxy)oct-4-ene-2,6-diyne ligand (bpod, 1). The thermal reactivities of these metalloenediynes are intimately modulated by metal oxidation state. Using differential scanning calorimetry (DSC), we demonstrate that the [Cu(bpod)(2)](+) complex (2) undergoes Bergman cyclization at 203 degrees C, whereas the Cu(II) analogue (3) is substantially more reactive and cyclizes at 121 OC. Similar results are also observed for mixed ligand [Cu(bpod)(pyridine)2](+/2+) analogues 4 (194 degrees C) and 5 (116 degrees C), suggesting that both complexes of a given oxidation state have comparable structures. The Cu(bpod)Cl-2 compound (6) exhibits a cyclization temperature (152 degrees C) midway between the those of Cu(I) and Cu(II) complexes, which can be explained by the propensity for cis-CuN2Cl2 structures to exhibit dihedral angle distortion. The oxidation-state-dependent thermal reactivity is unprecedented and reflects the influence of the ligand field geometry on the barrier to enediyne cyclization. On the basis of X-ray structures of Cu(pyridine)lt complexes, 2 and 4 are proposed to be tetrahedral. In contrast, the electronic absorption spectra of 3 and 5 each show a broad envelope that can be Gaussian resolved into three ligand field transitions characteristic of a Cu(II) center in a tetragonal octahedral environment. This structural assignment is confirmed by the EPR spin Hamiltonian parameters (g(parallel to)/A(parallel to) (cm) = 134 (3), 138 (5)) and is consistent with crystallographically characterized Cu(pyridine)(4)X-2 structures. Molecular mechanics calculations have independently derived comparable tetrahedral and tetragonal structures for 2 and 3, respectively, and determined the average alkyne termini separation to be [a] = 4.0 Angstrom for 2 and 3.6 Angstrom for 3. Thus, the tetrahedral geometries of the copper centers in 2 and 4 increase the distance between alkyne termini relative to the tetragonal Cu(II) geometries of 3 and 5, and are therefore responsible for the increase in the thermal cyclization temperatures. The DSC and spectroscopic data for 6 support these conclusions, as the latter suggests a distorted four-coordinate structure in the solid state, and a six-coordinate geometry in solution, which gives rise to an intermediate Bergman cyclization temperature. Overall, our results emphasize the utility of newly emerging metalloenediyne complexes for controlling thermal Bergman cyclization reactions and provide insights into designing novel, pharmacologically useful metalloenediyne compounds.

  DOI：

  10.1021/ja0017918
• 作为产物：
  描述：

  顺-1,2-二氯乙烯 、 哌喃 在 copper(l) iodide 、 四(三苯基膦)钯 、 正丁胺 作用下， 以 苯 为溶剂， 反应 13.0h， 以62%的产率得到(4Z)-1,8-bis-(tetrahydropyran-2-yloxy)-oct-4-ene-2,6-diyne
  参考文献：
  名称：

  新型无环烯二炔的合成与表征

  摘要：

  摘要 利用Sonogashira 耦合条件合成了一组新的对称和不对称无环烯二炔，并对其进行了光谱表征。补充材料可用于本文。转至出版商的 Synthetic Communications® 在线版以查看免费的补充文件。图形概要

  DOI：

  10.1080/00397911.2012.698355

文献信息

• 1,x-Elimination Reactions: Extending the Limits of a Classical Organic Reaction
  作者：Christian Werner、Henning Hopf、Ina Dix、Peter Bubenitschek、Peter G. Jones

  DOI：10.1002/chem.200700827

  日期：2007.11.26

  derivatives in which the two terminal carbon atom are separated by an unsaturated spacer unit ("pi spacer") undergo 1,x-elimination reactions (with x=6, 8, 10, and 14), using Mori's reagent (nBu3SnSiMe3/CsF). The resulting cumulenic intermediates cyclodimerize in a subsequent step yielding novel macrocyclic acetylenic and bridged aromatic compounds (cyclophanes). Thus 1,6-eliminations were carried out with dibromide

  使用森试剂，其中两个末端碳原子被不饱和间隔单元（“ pi spacer”）隔开的α，ω-二溴衍生物经历1，x消除反应（x = 6、8、10和14） （nBu3SnSiMe3 / CsF）。所得的异丙苯中间体在随后的步骤中环二聚，产生新的大环炔属和桥连的芳族化合物（环烷）。因此，用二溴化物17进行1,6-消除反应得到1,3,7,9-环十二碳酸酯（20），用苄基溴化物24进行环素26和27。通过1,8消除，16元大环化合物33可以由二烯化物31制备，苯甲酰化的1,5-环辛二炔41由二溴化物38制备，环烷酮45和46的混合物由前体43制备。成功地用二溴化物47，50进行1,10-消除，；和53产生相应的不饱和环烷（环戊烯）49、52和55。研究了溶剂对环二聚化47-＞ 49的影响，其中乙腈提供最高的收率。通过1,10消除前体二溴化物57a和b来获得杂物59a和b，在涉及二溴化物50和57b 1：
• Synthesis and Anticancer Activity of 13-Membered Cyclic Enediynes
  作者：Mukul Sharma、Mukesh C Joshi、Vineet Kumar、Sanjay V. Malhotra、Diwan S. Rawat

  DOI：10.1002/ardp.201000309

  日期：2011.9

  of 15 novel 13‐membered cyclic enediyne derivatives using simple and straightforward approach. Representative examples were screened for their anticancer activities on 60 different human tumor cell lines representing various histologies viz. leukemia, melanoma, and cancers of lung, colon, kidney, ovary, breast, prostate, and central nervous system. The enediyne derivatives with halogen substitutions

  我们在此描述了使用简单直接的方法合成 15 种新型 13 元环烯二炔衍生物。对代表各种组织学的 60 种不同人类肿瘤细胞系筛选了代表性实例的抗癌活性。白血病、黑色素瘤和肺癌、结肠癌、肾癌、卵巢癌、乳腺癌、前列腺癌和中枢神经系统癌。发现具有卤素取代的烯二炔衍生物，尤其是氟化物，对大多数细胞系具有活性。初步结果表明，对几种细胞系的肿瘤细胞生长有轻微到良好的抑制作用，这显示了这类化合物在抗癌应用方面的潜力。
• Photoisomerization as a trigger for Bergman cyclization: Synthesis and reactivity of azoenediynes
  作者：Moumita Kar、Amit Basak、Manish Bhattacharjee

  DOI：10.1016/j.bmcl.2005.09.005

  日期：2005.12

  Cyclic enediynes 1a and 2a containing stable E-azo moiety (azoenediynes) have been synthesized. These compounds upon irradiation with long wavelength UV isomerize to the Z-compounds 1b and 2b, which can be thermally reisomerized to the Z compounds. Reactivity studies toward BC using DSC predictably indicate higher reactivity for the Z-isomers. Our studies may provide a novel way to modulate the reactivity of enediynes under thermal or photochemical conditions. (c) 2005 Elsevier Ltd. All rights reserved.
• Koenig, Burkhard; Hollnagel, Helli; Ahrens, Birte, Angewandte Chemie, 1995, vol. 107, # 22, p. 2763 - 2765
  作者：Koenig, Burkhard、Hollnagel, Helli、Ahrens, Birte、Jones, Peter G.

  DOI：——

  日期：——
• Koenig, Burkhard; Pitsch, Wolfgang; Dix, Ina, Synthesis, 1996, # 4, p. 446 - 448
  作者：Koenig, Burkhard、Pitsch, Wolfgang、Dix, Ina、Jones, Peter G.

  DOI：——

  日期：——