1-(allyloxy)-2-octyne | 140605-60-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-(allyloxy)-2-octyne
• 英文别名: 1-allyloxyoct-2-yne；allyl oct-2-ynyl ether；allyl 2-octynyl ether；1-Prop-2-enoxyoct-2-yne
• CAS: 140605-60-3
• 化学式: C₁₁H₁₈O
• 分子量: 166.263
• InChiKey: FPTAQOMPPBNAPN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  12
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 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)-2-octyne 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以100%的产率得到undec-1-en-5-yn-4-ol
  参考文献：
  名称：

  Radical cyclization of (bromomethyl)dimethylsilyl propargyl ethers. Regio-, chemo- and stereoselectivity.

  摘要：

  Radical cyclization of (bromomethyl)dimethylsilyl propargyl ether derivatives 1 is a powerful reaction with a high degree of regio-, chemo-, and stereoselectivity. Trisubstituted olefins 3, cyclopentene derivatives 5, and diquinane system 7j are obtained in good yields by a judicious choice of unsaturated substituents. Triquinane frameworks could be obtained stereoselectively from a suitable acyclic substrate of type 1 in a one-pot reaction. First attempts have not yet allowed us to aim at this goal due to interesting (1,5) hydrogen transfers. Moreover, we have intercepted, for the first time, the alpha-cyclopropyl radical which is involved in the Stork-Beckwith mechanism of the 5-versus 6-membered ring formation in the vinyl radical cyclization.

  DOI：

  10.1021/jo00037a026
• 作为产物：
  描述：

  2-辛炔-1-醇 、 3-溴丙烯 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 3.5h， 以39%的产率得到1-(allyloxy)-2-octyne
  参考文献：
  名称：

  系链烯烃在镍催化添加到炔烃中的配体可切换导向效应

  摘要：

  描述了醛与包含系链烯烃的炔烃的镍催化还原偶联，其中区域选择性的程度和意义由系链的长度和添加剂的存在或不存在控制。当炔烃和烯烃被四个键分开时，观察到非常高（> 95:5）的区域选择性。使用单齿膦作为添加剂导致以相等和相反的选择性（5：> 95）形成相反的区域异构体。这些结果为在区域选择性决定步骤中远程烯烃和金属中心之间的相互作用提供了强有力的证据，并表明有和没有添加剂的反应通过根本不同的机制进行。

  DOI：

  10.1021/ja0446799

文献信息

• Ligand-Switchable Directing Effects of Tethered Alkenes in Nickel-Catalyzed Additions to Alkynes
  作者：Karen M. Miller、Timothy F. Jamison

  DOI：10.1021/ja0446799

  日期：2004.12.1

  Nickel-catalyzed reductive couplings of aldehydes with alkynes that contain tethered olefins are described, in which the degree and sense of regioselectivity are controlled by the length of the tether and the presence or absence of an additive. When the alkyne and alkene are separated by four bonds, very high (>95:5) regioselectivities are observed. Use of a monodentate phosphine as an additive leads

  描述了醛与包含系链烯烃的炔烃的镍催化还原偶联，其中区域选择性的程度和意义由系链的长度和添加剂的存在或不存在控制。当炔烃和烯烃被四个键分开时，观察到非常高（> 95:5）的区域选择性。使用单齿膦作为添加剂导致以相等和相反的选择性（5：> 95）形成相反的区域异构体。这些结果为在区域选择性决定步骤中远程烯烃和金属中心之间的相互作用提供了强有力的证据，并表明有和没有添加剂的反应通过根本不同的机制进行。
• Rhodium-Catalyzed Asymmetric Cyclization/Hydroboration of 1,6-Enynes
  作者：Robert E. Kinder、Ross A. Widenhoefer

  DOI：10.1021/ol052986t

  日期：2006.5.1

  [reaction: see text] Reaction of enyne 1 with catecholborane catalyzed by a 1:1 mixture of [Rh(COD)(2)](+)SbF(6)(-) and (S)-BINAP (5 mol %) followed by Pd-catalyzed arylation with p-IC(6)H(4)CF(3) gave benzylidenecyclopentane 5 in 65% yield with 88% ee. Rhodium-catalyzed asymmetric cyclization/hydroboration followed either by Pd-catalyzed arylation or by oxidation was applied to the synthesis of a

  [反应：参见文本] [Rh（COD）（2）]（+）SbF（6）（-）和（S）-BINAP（5摩尔％）1：1混合物催化的烯炔1与儿茶酚硼烷的反应然后用p-IC（6）H（4）CF（3）进行Pd催化的芳基化反应，得到亚苄基环戊烷5，产率为65％，ee为88％。铑催化的不对称环化/氢硼化，然后钯催化的芳基化或氧化，被用于合成许多手性，非外消旋的碳环和杂环。
• Trapping bicyclic titanacyclopentenes with bis(trichloromethyl) carbonate (BTC): a new method to bicyclic cyclopentenones
  作者：Zongbao Zhao、Yu Ding

  DOI：10.1039/a708182k

  日期：——

  Bis(trichloromethyl) carbonate is found to trap bicyclic titanacyclopentenes providing a new method for bicyclization of enynes into bicyclic cyclopentenones.

  发现碳酸二（三氯甲基）酯可捕获双环钛环戊烯，这为将烯炔双环化为双环环戊烯酮提供了一种新方法。
• Use of fused ring cyclopentanones and cyclopentenones in controlling plant growth
  申请人：The University of Strathclyde

  公开号：US06174840B1

  公开（公告）日：2001-01-16

  Use in inhibiting plant growth of a compound of formula II in which either the pair of symbols X and Y or the pair of symbols Y and Z, together with the carbon atoms to which they are attached, form a non-aromatic ring system having either 5 or 7 ring atoms, all of which are carbon except that one may be oxygen, and which is substituted or unsubstituted, R1 represents a hydrogen atom or an alkyl, alkenyl or a substituted or unsubstituted phenyl group and R2 represents a hydrogen atom and R3 an alkyl carboxyalkyl group or R2 and R3 together form a double bond, and thereafter any unsatisfied valencies of ring carbon atoms of the ring shown in formula II are satisfied by hydrogen atoms.

  使用公式II中的化合物抑制植物生长，其中符号X和Y或符号Y和Z中的一对，与它们附着的碳原子一起，形成一个非芳香环系统，其具有5个或7个环原子，所有原子都是碳原子，除了一个可能是氧原子，并且被取代或未取代，R1代表氢原子或烷基，烯基或取代或未取代的苯基团，R2代表氢原子，R3代表烷基羧基烷基团或R2和R3共同形成双键，然后公式II中环的任何未满足的碳原子的价键都由氢原子满足。
• 2,2′‐Bis[bis(3,5‐di‐<i>tert</i>‐butyl‐4‐methoxyphenyl)phosphino]‐6,6′‐dimethoxy‐1,1′‐biphenyl in Intramolecular Rhodium(I)‐Catalyzed Asymmetric Pauson–Khand‐Type Reactions
  作者：Dong Eun Kim、Virginie Ratovelomanana‐Vidal、Nakcheol Jeong

  DOI：10.1002/adsc.201000221

  日期：2010.10.9

  AbstractA cationic rhodium(I)/2,2′‐bis[bis(3,5‐di‐tert‐butyl‐4‐methoxyphenyl)phosphino]‐6,6′‐dimethoxy‐1,1′‐biphenyl (DTBM‐MeO‐BIPHEP) catalyst was highly efficient for the asymmetric catalytic Pauson–Khand reaction, especially for those substrates containing aryl group‐substituted alkynes. The formation of the products that were derived from a β‐hydride eliminated intermediate 5 was completely suppressed over a wide range of substrates. This reaction was a serious process competing reaction with the migratory CO insertion that led to the Pauson–Khand reaction product and often substantially ruined the chemical yield of the Pauson–Khand reaction. The advantages of this system were clearly demonstrated for previously troublesome substrates, N‐tosyl‐ (1b) and malonate‐tethered 1,6‐enynes (1c), that exhibited a higher enantioselectivity without a loss in the chemical yields. The obvious beneficial effects were attributed to the synergic effect of various factors, such as the electron density of the phosphorus of the ligand, the dihedral angles of the atropisomeric ligand, and the substitution on the phosphine aryl rings which play a crucial role in the stereochemical outcome of Rh‐catalyzed Pauson–Khand reaction.