1-bromo-5-oxaocta-2,7-diyne | 630400-79-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-bromo-5-oxaocta-2,7-diyne
• 英文别名: 1-Bromo-4-prop-2-ynoxybut-2-yne
• CAS: 630400-79-2
• 化学式: C₇H₇BrO
• 分子量: 187.036
• InChiKey: GHLDXSOCJDCGQN-UHFFFAOYSA-N

物化性质

• 沸点：
  240.7±25.0 °C(Predicted)
• 密度：
  1.431±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  1-bromo-5-oxaocta-2,7-diyne 在 sodium hydride 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 生成 4,4-bis(carbethoxy)-9-oxatridec-1-ene-6,11-diyne
  参考文献：
  名称：

  铑配合物催化烯二炔的硅引发羰基化碳三环化和[2+2+2+1]环加成反应

  摘要：

  dodec-11-ene-1,6-diynes 或它们的杂原子同系物与由 Rh(acac)(CO)2 催化的氢硅烷在环境温度和 CO 压力下反应得到相应的稠合 5-7-5 三环产物， 5-oxo-1,3a,4,5,7,9-hexahydro-3H-cyclopenta[e]azulenes 或它们的杂原子同系物，通过独特的硅引发的级联羰基化碳三环化 (CO-SiCaT) 工艺以优异的产率获得。还发现5-7-5稠合三环产物可以通过新型的分子内[2+2+2+1]环加成过程由相同类型的烯二炔和CO获得。讨论了这两种三环化过程的特点及其反应机理的根本区别。这种新型的高级环加成反应也已成功应用于 undeca-5 的三环化反应，10-diyn-1-als，提供相应的带有七元内酯部分的 5-7-5 稠环产物。还讨论了烯二炔和二炔底物的相关 [2+2+2] 三环化。这些新发现的反应可以同时构建多个键，在

  DOI：

  10.1021/ja054221m
• 作为产物：
  描述：

  4-(prop-2-yn-1-yloxy)but-2-yn-1-ol 在 四溴化碳 、 三苯基膦 作用下， 生成 1-bromo-5-oxaocta-2,7-diyne
  参考文献：
  名称：

  Ene-yne-ene and ene-yne-yne metathesis of norbornene derivatives

  摘要：

  Norbornene derivatives 4 and 5 containing sidechains bearing an internal alkyne and either a terminal alkene or a terminal alkyne were found to undergo a cascade of metathesis reactions when treated with ruthenium based metathesis catalysts to form highly functionalised pentacyclic products. The reactions illustrate an interesting difference in reactivity between Grubbs' catalyst and the second generation catalyst, with the former being more reactive for the early steps of the cascade. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.09.035

文献信息

• Ruthenium-Catalyzed Cycloaddition of 1,6-Diynes and Nitriles under Mild Conditions: Role of the Coordinating Group of Nitriles
  作者：Yoshihiko Yamamoto、Keisuke Kinpara、Ryuji Ogawa、Hisao Nishiyama、Kenji Itoh

  DOI：10.1002/chem.200600176

  日期：2006.7.17

  to afford bicyclic pyridines. Careful screening of nitrile components revealed that a C[triple chemical bond]C triple bond or heteroatom substituents, such as methoxy and methylthio groups, proved to act as the coordinating groups, whereas C==C or C==O double bonds and amino groups failed to promote cycloaddition. This suggests that coordinating groups with multiple pi-bonds or lone pairs are essential

  在催化量的[Cp * RuCl（cod）]（Cp * =五甲基环戊二烯，cod = 1,5-环辛二烯）的存在下，使1,6-二炔与带有配位基团的腈发生化学和区域选择性反应在室温下，例如二氰化物或α-卤代腈，得到双环吡啶。仔细筛选腈成分显示，证明C [三化学键] C三键或杂原子取代基（例如甲氧基和甲硫基）充当配位基团，而C == C或C == O双键和氨基团体未能促进环加成反应。这表明具有多个π键或孤对的配位基团对于腈组分是必不可少的。
• Air-Stable {(C₅H₅)Co} Catalysts for [2+2+2] Cycloadditions
  作者：Anaïs Geny、Nicolas Agenet、Laura Iannazzo、Max Malacria、Corinne Aubert、Vincent Gandon

  DOI：10.1002/anie.200806001

  日期：2009.2.23

  Cobalt cyclopentadienyl complexes incorporating a fumarate and a CO ligand (see picture) efficiently catalyze inter‐ and intramolecular [2+2+2] cycloadditions of alkynes, nitriles, and/or alkenes to give benzenes, pyridines, or 1,3‐cyclohexadienes. Unlike catalysts such as [CpCo(CO)2] or [CpCo(C2H4)2] (Cp=C5H5), they are air‐stable, easy to handle, compatible with microwave conditions, and do not necessarily

  结合富马酸酯和CO配体的环戊二烯钴复合物（见图）有效地催化炔烃，腈和/或烯烃的分子间和分子内[2 + 2 + 2]环加成反应，从而生成苯，吡啶或1,3-环己二烯。与[CpCo（CO）2 ]或[CpCo（C 2 H 4）2 ]（Cp = C 5 H 5）等催化剂不同，它们具有空气稳定性，易于处理，与微波条件兼容，并且不一定需要辐射才能活跃。
• The Synthesis of Highly Substituted Cyclooctatetraene Scaffolds by Metal-Catalyzed [2+2+2+2] Cycloadditions: Studies on Regioselectivity, Dynamic Properties, and Metal Chelation
  作者：Paul A. Wender、Justin P. Christy、Adam B. Lesser、Marc T. Gieseler

  DOI：10.1002/anie.200903859

  日期：2009.9.28

  All‐kynes of COTs: A Ni0‐catalyzed [2+2+2+2] cycloaddition of 1,6‐diynes yields highly functionalized hexa‐ and octa‐substituted cyclooctatetraenes (COTs; see picture) along with the first example of a fully intramolecular [2+2+2+2] cycloaddition product. The regioselectivity of this process is studied and the initial use of COT ligands is shown in the formation of a ZnII complex with a bis(oxazoline)

  COT的全酮：Ni 0催化的1，6-二炔的[2 + 2 + 2 + 2]环加成反应生成高度官能化的六和八取代的环辛烯（COT；参见图片），以及完全分子内的[2 + 2 + 2 + 2]环加成产物。研究了该方法的区域选择性，并在与双（恶唑啉）COT形成Zn II配合物时显示了COT配体的最初用途。
• A [2 + 2 + 2]-Cycloaddition Approach toward 6-Oxa-allocolchicinoids with Apoptosis-Inducing Activity
  作者：Norman Nicolaus、Susanne Strauss、Jörg-Martin Neudörfl、Aram Prokop、Hans-Günther Schmalz

  DOI：10.1021/ol802542c

  日期：2009.1.15

  Following an A -> ABC strategy, a new synthesis of 6-oxa-allocolchicinoids was developed exploiting a microwave-promoted Co- or Rh-catalyzed intramolecular [2 + 2 + 2]-cycloaddition (alkyne cyclotrimerization) as a key step. The approach opens a short and efficient access to a variety of novel compounds, some of which were found to exhibit significant and selective apoptosis-inclucing activities against BJAB tumor cells.
• Ene–yne metathesis of polyunsaturated norbornene derivatives
  作者：Donatella Banti、Elisabetta Groaz、Michael North

  DOI：10.1016/j.tet.2004.06.114

  日期：2004.9

  Norbornene derivatives bearing endo-substituents in the 5- and 6-positions were studied as substrates for ene-yne metathesis cascades. Substrates which contained an internal alkyne and a terminal alkene or alkyne in each sidechain were found to undergo a metathesis cascade leading to pentacyclic bis-dienes and bis-trienes. Attempts to extend the chemistry further to sidechains containing two internal alkynes or two internal alkynes and a terminal alkene were not successful with the first generation Grubbs' catalyst. However, the substrate containing two internal alkynes did react with the second generation Grubbs' catalyst to give a tetra-diene containing product. (C) 2004 Elsevier Ltd. All rights reserved.