2-(1-phenethylprop-2-ynyloxy)ethanol | 216986-44-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-(1-phenethylprop-2-ynyloxy)ethanol
• 英文别名: 2-[(5-phenylpent-1-yn-3-yl)oxy]ethanol；2-(5-Phenylpent-1-yn-3-yloxy)ethanol
• CAS: 216986-44-6
• 化学式: C₁₃H₁₆O₂
• 分子量: 204.269
• InChiKey: SJUWFCVYMYALES-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(1-phenethylprop-2-ynyloxy)ethanol 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 18.0h， 生成 7-phenyl-2-oxabicyclo[3.3.0]oct-6-ene
  参考文献：
  名称：

  Generation of Cycloalkylidene Carbenes via Exo-Type Cyclization of Alkynyllithiums Bearing Remote Leaving Group

  摘要：

  The reaction of 5-hexynyl tosylate (3a) with alkynyllithium (RC=CLi; R Ph, TMS) gives enynes 5 and 6. The reaction proceeds through a mechanism involving a novel exo-type cyclization of 6-lithiod-hexynyl tosylate to form cyclopentylidene carbene. Enyne 6 is produced by the addition of RC=CLi to the carbene, whereas rearrangement of the carbene to cyclohexyne followed by carbolithiation with RC=CLi gives enyne 5. The formation of cyclopentylidene carbene and cyclohexyne as intermediates is clearly demonstrated by trapping experiments with cyclohexene land triethylsilane) and with 1,3-diphenylisobenzofuran, respectively. Alkynyllithiums derived from 3-butynyl and 6-heptynyl p-fluorobenzenesulfonates (19a,b) undergo a similar exo-type cyclization to give cyclopropylidene and cyclohexylidene carbenes, respectively.

  DOI：

  10.1021/jo981411p
• 作为产物：
  描述：

  ethyl (1-ethynyl-3-phenylpropoxy)acetate 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 16.0h， 以2.22 g的产率得到2-(1-phenethylprop-2-ynyloxy)ethanol
  参考文献：
  名称：

  铜（I）催化炔丙基醚和胺的区域和立体选择性分子内烷基硼化

  摘要：

  已经开发了铜（I）催化带有烷基亲电部分的炔丙基醚和胺的区域和立体选择性分子内烷基化。该反应显示出高的官能团耐受性并得到带有杂环的高度官能化的烯基硼酸酯，其在有机化学中是通用的合成中间体。硼酸酯化产物可以通过立体有择的转化而转化为多取代的烯烃。机理研究表明，铜（I）催化的硼酸酯化反应的化学和立体选择性取决于离去基团的类型。

  DOI：

  10.1021/acs.joc.7b02071

文献信息

• Cyclization of Gold Acetylides: Synthesis of Vinyl Sulfonates via Gold Vinylidene Complexes
  作者：Janina Bucher、Thomas Wurm、Kumara Swamy Nalivela、Matthias Rudolph、Frank Rominger、A. Stephen K. Hashmi

  DOI：10.1002/anie.201310280

  日期：2014.4.7

  Differently substituted terminal alkynes that bear sulfonate leaving groups at an appropriate distance were converted in the presence of a propynyl gold(I) precatalyst. After initial formation of a gold acetylide, a cyclization takes place at the β‐carbon atom of this species. Mechanistic studies support a mechanism that is related to that of dual gold‐catalyzed reactions, but for the new substrates

  在丙炔基金（I）预催化剂的存在下，将具有适当距离的磺酸盐离去基团的不同取代的末端炔烃进行了转化。乙炔化金最初形成后，在该物种的β-碳原子上发生环化。机理研究支持一种与双重金催化反应相关的机制，但对于新的底物，仅需一个金原子即可激活底物。形成亚乙烯基金络合物后，它与磺酸盐的离去基团形成紧密的接触离子对，这两个部分的重组产生了乙烯基磺酸盐，这是有价值的目标，可以用作例如交叉偶联反应的前体。
• Carbocyclization Reaction of ω-Iodo- and 1,ω-Diiodo-1-alkynes without the Loss of Iodine Atoms through a Carbenoid-Chain Process
  作者：Toshiro Harada、Keiko Muramatsu、Kenta Mizunashi、Chie Kitano、Daisuke Imaoka、Takayuki Fujiwara、Hiroshi Kataoka

  DOI：10.1021/jo7021179

  日期：2008.1.1

  give (diiodomethylene)cycloalkanes. The diiodomethylene products are also obtained by iodine atom-transfer-type cyclization of ω-iodo-1-alkynes, using 1-iodo-1-hexyne as an external iodine atom source. Bromine atom-transfer and proton-transfer cyclization proceed as well by employing 1-bromo-1-octyne and 1-octyne, respectively. These reactions are proposed to proceed through a carbenoid-chain process

  描述了ω-碘-1-炔和1，ω-二碘-1-炔的原子经济碳环化反应，得到的产品中掺入了碘原子。通过催化量的LDA引发2-（2-丙炔氧基）乙基碘的环异构化，从而以高收率得到3-（碘亚甲基）四氢呋喃。用催化量的1-己炔基锂处理后，1，ω-二碘-1-炔烃有效地进行环异构化，得到（二碘亚甲基）环烷烃。二碘亚甲基产物也可以通过使用1-碘-1-己炔作为外部碘原子源，通过ω-碘-1-炔烃的碘原子转移型环化获得。分别通过使用1-溴-1-辛炔和1-辛炔来进行溴原子转移和质子转移环化。建议这些反应通过类胡萝卜素链过程进行，该过程涉及外的乙炔锂中间体-cyclization给力，我亚烷基卡宾。结果表明，该外型-cyclization立体专一性进行通过立体化学的反转在亲电子碳。
• Copper(I)-Catalyzed Regio- and Stereoselective Intramolecular Alkylboration of Propargyl Ethers and Amines
  作者：Hiroaki Iwamoto、Yu Ozawa、Koji Kubota、Hajime Ito

  DOI：10.1021/acs.joc.7b02071

  日期：2017.10.6

  transformed into multisubstituted alkenes through stereospecific transformations. Mechanistic studies showed that the chemo- and stereoselectivity of copper(I)-catalyzed borylation depends on the type of leaving group. Density functional theory calculations suggested that the regioselectivity of the borylcupration of the alkyne is controlled by the electronic effect of the oxygen atom of the propargyl ether

  已经开发了铜（I）催化带有烷基亲电部分的炔丙基醚和胺的区域和立体选择性分子内烷基化。该反应显示出高的官能团耐受性并得到带有杂环的高度官能化的烯基硼酸酯，其在有机化学中是通用的合成中间体。硼酸酯化产物可以通过立体有择的转化而转化为多取代的烯烃。机理研究表明，铜（I）催化的硼酸酯化反应的化学和立体选择性取决于离去基团的类型。
• Generation of Cycloalkylidene Carbenes via Exo-Type Cyclization of Alkynyllithiums Bearing Remote Leaving Group
  作者：Toshiro Harada、Katsuhiro Iwazaki、Takeshi Otani、Akira Oku

  DOI：10.1021/jo981411p

  日期：1998.11.1

  The reaction of 5-hexynyl tosylate (3a) with alkynyllithium (RC=CLi; R Ph, TMS) gives enynes 5 and 6. The reaction proceeds through a mechanism involving a novel exo-type cyclization of 6-lithiod-hexynyl tosylate to form cyclopentylidene carbene. Enyne 6 is produced by the addition of RC=CLi to the carbene, whereas rearrangement of the carbene to cyclohexyne followed by carbolithiation with RC=CLi gives enyne 5. The formation of cyclopentylidene carbene and cyclohexyne as intermediates is clearly demonstrated by trapping experiments with cyclohexene land triethylsilane) and with 1,3-diphenylisobenzofuran, respectively. Alkynyllithiums derived from 3-butynyl and 6-heptynyl p-fluorobenzenesulfonates (19a,b) undergo a similar exo-type cyclization to give cyclopropylidene and cyclohexylidene carbenes, respectively.