1-(allyloxy)-4-bromobut-2-yne | 216856-88-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-(allyloxy)-4-bromobut-2-yne
• 英文别名: 2-Butyne, 1-bromo-4-(2-propenyloxy)-；1-bromo-4-prop-2-enoxybut-2-yne
• CAS: 216856-88-1
• 化学式: C₇H₉BrO
• 分子量: 189.052
• InChiKey: OUOOIKUTIFTWFA-UHFFFAOYSA-N

物化性质

• 沸点：
  225.8±25.0 °C(Predicted)
• 密度：
  1.331±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  9
• 可旋转键数：
  3
• 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-(allyloxy)-4-bromobut-2-yne 在 氢氧化钾 、 四溴化碳 、 sodium hydride 、 二甲基亚砜 、 三苯基膦 作用下， 以 乙醚 、 N,N-二甲基甲酰胺 为溶剂， 反应 45.0h， 生成
  参考文献：
  名称：

  Ene–yne metathesis of polyunsaturated norbornene derivatives

  摘要：

  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.

  DOI：

  10.1016/j.tet.2004.06.114
• 作为产物：
  描述：

  4-(allyloxy)but-2-yn-1-ol 在 吡啶 、 三溴化磷 作用下， 以 乙醚 为溶剂， 反应 19.0h， 以62%的产率得到1-(allyloxy)-4-bromobut-2-yne
  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

文献信息

• Synthesis of Cyclic and Macrocyclic Ethers Using Metathesis Reactions of Alkenes and Alkynes
  作者：Elisabetta Groaz、Donatella Banti、Michael North

  DOI：10.1002/ejoc.200700291

  日期：2007.8

  norbornene esters, leading to 6,12-fused cycloalkynes which would subsequently undergo further enyne and/or alkene metatheses. This culminated in the development of the first one-pot metathesis process in which alkyne, enyne and alkene metathesis reactions initiated by two different catalysts all occur sequentially to form a 5,12-fused bicyclic diene product. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim

  已经研究了带有烯丙基和/或炔丙基醚取代基的环己烷和环己烯的复分解转化。使用第一代和第二代明确定义的亚烷基钌催化剂获得了一系列含有稠合 6,8-双环系统的产物，这些产物由烯烃和/或烯炔复分解产生。然而，无应变的环己烯单元不参与任何这些复分解过程，即使这样做会导致热力学更稳定的产品。这与之前对类似化合物和相应的氨基取代环己烯的结果形成对比。还报道了通过涉及合适环己烯醚侧链的复分解过程合成二烯和二氢呋喃。当无应变的环己烯单元被降冰片烯基团取代时，紧张的烯烃确实参与了烯烃和烯炔复分解的级联反应。这种化学反应扩展到环己烯和降冰片烯酯的炔烃复分解反应，产生 6,12-稠合的环炔烃，随后将进行进一步的烯炔和/或烯烃复分解反应。这最终导致了第一个单锅复分解过程的发展，在该过程中，由两种不同催化剂引发的炔烃、烯炔和烯烃复分解反应依次发生，形成 5,12-稠合双环二烯产物。(© Wiley-VCH Verlag
• Indium-mediated annulation of 2-azidoaryl aldehydes with propargyl bromides to [1,2,3]triazolo[1,5-<i>a</i>]quinolines
  作者：Xiaomin Zhang、Jiali Yang、Ni Xiong、Zhe Han、Xinhua Duan、Rong Zeng

  DOI：10.1039/d1ob01183a

  日期：——

  indium-mediated cascade annulation reaction of 2-azidoaryl aldehydes with propargyl bromides is reported. The aromatic 5/6/6-fused heterocycles, [1,2,3]triazolo[1,5-a]quinoline derivatives, could be constructed in one pot in moderate yields with a broad substrate scope. Mechanistic studies indicated that the reaction proceeded through allenol formation, azide–allene [3 + 2] cycloaddition, and dehydration

  报道了一种有效的铟介导的 2-叠氮芳基醛与炔丙基溴的级联环化反应。芳香族 5/6/6-稠合杂环，[1,2,3]三唑并[1,5- a ]喹啉衍生物，可以在一锅中以中等产率和广泛的底物范围构建。机理研究表明，该反应通过丙二烯醇形成、叠氮-丙二烯[3 + 2]环加成和脱水进行。还探索了产品的合成潜力，包括脱氮功能化和 Pd 催化的偶联反应。
• Facile Synthesis of Bicyclic and Tricyclic Skeletons by Cycloisomerizations of Hept-1-en-6-ynes and 4,9-Diheteradodeca-1,11-dien-6-ynes, Followed by [4 + 2] Cycloadditions
  作者：Lonneke J. van Boxtel、Stefanie Körbe、Mathias Noltemeyer、Armin de Meijere

  DOI：10.1002/1099-0690(200106)2001:12<2283::aid-ejoc2283>3.0.co;2-g

  日期：2001.6

  reaction with methyl acrylate, occurred with intramolecular transesterification to give the tricyclic lactones 11 (37%) and 16 (15%), respectively. Tricyclic systems containing up to three heteroatoms could be obtained from the corresponding dodeca-1,11-dien-6-ynes, by palladium-catalyzed cycloisomerization followed by intramolecular [4 + 2] cycloaddition. The scope and limitations of this single-operation

  钯催化的各种 4-取代庚基-1-烯-6-炔的分子内交叉偶联，然后与丙烯酸甲酯和 2-氯-2-亚环丙基乙酸酯的分子间 [4 + 2] 环加成产生全碳和杂类似双环衍生物8、9、18、19 和 24 (24-71%)。羟甲基和羟乙基取代的庚基-1-烯-6-炔 5 和 15 的环异构化，然后是与丙烯酸甲酯的 Diels-Alder 反应，发生分子内酯交换，得到三环内酯 11 (37%) 和 16 (15 ％）， 分别。通过钯催化的环异构化和分子内 [4 + 2] 环加成反应，可以从相应的 dodeca-1,11-dien-6-yne 中获得最多包含三个杂原子的三环系统。评估了这种单操作三环化的范围和局限性。具有两个氮或两个氧原子的对称双取代二炔以这种方式有效反应 (41-90%)，产生 5-6-5 环大小组合。所有情况下的非对映选择性都很差（1:1 到 3.4:1）。不对称双取代的 dodeca-1
• Rapid Entry into Mono-, Bi-, and Tricyclic β-Lactam Arrays via Alkene Metathesis
  作者：Anthony G. M. Barrett、Simon P. D. Baugh、D. Christopher Braddock、Kevin Flack、Vernon C. Gibson、Matthew R. Giles、Edward L. Marshall、Panayiotis A. Procopiou、Andrew J. P. White、David J. Williams

  DOI：10.1021/jo981150j

  日期：1998.10.1

  4-Acetoxy-2-azetidinone and (3R,4R)-4-acetoxy-3-[(1R)-1-(tert-butyldimethylsilyl)-oxyethyl]-2-azetidinone were converted into 4-alkenyloxy-, 4-(N-allyltoluene-4-sulfonamido)-, 4-(allylthio)-, and 4-alkenyl-2-azetidinone systems. In addition, 4-acetoxy-2-azetidinone and (3R,4R)-4-acetoxy-3-[(1R)-1-(tert-butyldimethylsilyl)-oxyethyl]-2-azetidinone were converted into beta-lactam dienes via sequential C-4 substitution using unsaturated alcohols, allyl mercaptan, N-allyltoluene-4-sulfonamide, and allyl(chloro)dimethylsilane followed by N-allylation. Crossed metathesis of beta-lactam alkenes with styrene partners and ring closing metathesis of beta-lactam dienes using the Schrock [(CF3)(2)MeCO](2)Mo(=CHCMe2Ph)(=NC6H3-2,6-iso-Pr-2) (1) or Grubbs Cl-2(Cy3P)(2)Ru=CHPh (2) carbenes gave diverse monocyclic and bicyclic beta-lactam systems including derivatives of 1-azabicyclo[4.2.0]octan-8-one, 1-azabicyclo[5.2.0]nonan-9-one and its 6-thia, 6-aza, and 6-oxa analogues, 7-oxa-1-azabicyclo[6.2.0]octan-10-one, 8-oxa-1-azabicyclo[7.2.0]octan-11-one, and 9-oxa-1-azabicyclo[8.2.0]octan-12-one. Ring-closing enyne metathesis and tandem ring-closing enyne and diene metathetic reactions were used to produce bicyclic beta-lactam conjugated dienes as exemplified by the conversion of (3S,4R)-(-)-3-[(1R)-(tert-butyldimethylsilyl)oxyethyl]-1-(5-oxa-oct-7-en-2-yn-1-yl)-4-(2-propenyl)-azetidin-2-one (83) into (6R,7S)-(+)-7-[(1R)-(tert-butyldimethylsilyl)oxyethyl]-3-[(2,5-dihydro)-3-furanyl]-1-azabicyclo[4.2.0]oct-3-en-8-one (98).
• Ene-yne-ene and ene-yne-yne metathesis of norbornene derivatives
  作者：Donatella Banti、Michael North

  DOI：10.1016/j.tetlet.2003.09.035

  日期：2003.10

  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.