1'-Methyl-2'-propenyl 2-propynoate | 161093-73-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 1'-Methyl-2'-propenyl 2-propynoate
• 英文别名: But-3-en-2-yl prop-2-ynoate
• CAS: 161093-73-8
• 化学式: C₇H₈O₂
• 分子量: 124.139
• InChiKey: DJCPQMDIVAIRSV-UHFFFAOYSA-N

物化性质

• 沸点：
  163.0±19.0 °C(Predicted)
• 密度：
  0.979±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1'-Methyl-2'-propenyl 2-propynoate 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex lithium bromide 、 copper(ll) bromide 作用下， 以 溶剂黄146 为溶剂， 反应 10.0h， 生成 cis-α-(E)-(Bromomethylene)-β-(bromomethyl)-γ-methyl-γ-butyrolactone 、 trans-α-(E)-(Bromomethylene)-β-(bromomethyl)-γ-methyl-γ-butyrolactone
  参考文献：
  名称：

  Palladium-Templated Regio- and Stereoselective Cyclization of 2'-Alkenyl 2-Alkynoates and Its Synthetic Applications

  摘要：

  2'-Alkenyl 2-alkynoates undergo facile stereoselective cyclization to alpha-(haloalkylidene)-gamma-butyrolactones upon treatment with a catalytic amount of palladium complex in the presence of CuX(2) and LiX. When an alkyl group is introduced to the 1'-position of the alkenyl group, unsubstituted 2-propynoates mainly give trans-beta, gamma-disubstituted gamma-lactones, and substituted 2-propynoates afford cis-beta,gamma-disubstituted gamma-lactones. Further elaborations of the halogen atoms and the synthesis of A-factor using this method are exemplified.

  DOI：

  10.1021/jo00110a018
• 作为产物：
  描述：

  3-丁烯-2-醇 、 丙炔酸 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 生成 1'-Methyl-2'-propenyl 2-propynoate
  参考文献：
  名称：

  钯（II）催化环化立体选择性合成对映体纯的β，γ-二取代的α-亚烷基γ-丁内酯

  摘要：

  在CuX 2和LiX的存在下，通过Pd（II）催化，由Pd（II）催化的易于合成的手性均烯丙基2-炔酸酯以光学活性形式合成具有顺式或反式构型的β，γ-二取代α-亚烷基-γ-丁内酯。

  DOI：

  10.1016/0957-4166(95)00009-e

文献信息

• Stereoselective synthesis of enantiopure β, γ-disubstituted α-alkylideneγ-butyrolactones via A palladium(II) catalyzed cyclization
  作者：Guoxin Zhu、Xiyan Lu

  DOI：10.1016/0957-4166(95)00009-e

  日期：1995.2

  β, γ-disubstituted α-alkylidene-γ-butyrolactones with cis or trans relative configurations were synthesized in both optically active forms from readily available homochiral allylic 2-alkynoates by Pd(II) catalysis in the presence of CuX2 and LiX.

  在CuX 2和LiX的存在下，通过Pd（II）催化，由Pd（II）催化的易于合成的手性均烯丙基2-炔酸酯以光学活性形式合成具有顺式或反式构型的β，γ-二取代α-亚烷基-γ-丁内酯。
• Palladium-Templated Regio- and Stereoselective Cyclization of 2'-Alkenyl 2-Alkynoates and Its Synthetic Applications
  作者：Jianguo Ji、Chunming Zhang、Xiyan Lu

  DOI：10.1021/jo00110a018

  日期：1995.3

  2'-Alkenyl 2-alkynoates undergo facile stereoselective cyclization to alpha-(haloalkylidene)-gamma-butyrolactones upon treatment with a catalytic amount of palladium complex in the presence of CuX(2) and LiX. When an alkyl group is introduced to the 1'-position of the alkenyl group, unsubstituted 2-propynoates mainly give trans-beta, gamma-disubstituted gamma-lactones, and substituted 2-propynoates afford cis-beta,gamma-disubstituted gamma-lactones. Further elaborations of the halogen atoms and the synthesis of A-factor using this method are exemplified.
• Preparation and Carbocupration–Silylation of Allyl Propiolates: Vicinal Functionalization To Form Polysubstituted (E)-Vinylic Silanes
  作者：Timothy S. Snowden、Cameron D. Massey、Michael P. Jennings

  DOI：10.1055/a-2186-6964

  日期：2024.1

  The preparation and TMSOTf-mediated catalytic carbocupration–silylation of allylic propiolates has been investigated, expanding on previous syntheses of a variety of β-alkyl- and β-aryl-substituted vinylsilanes from an ethyl propiolate precursor. With few exceptions, the series of synthesized O-allyl (E)-vinylsilanes has been isolated in high yields (61–89%) with exceptional diastereoselectivities

  研究了烯丙基丙炔酸酯的制备和 TMSOTf 介导的催化碳铜化-硅烷化反应，扩展了之前从丙炔酸乙酯前体合成各种 β-烷基和 β-芳基取代的乙烯基硅烷的方法。除少数例外，一系列合成的O-烯丙基 ( E )-乙烯基硅烷已以高收率 (61–89%) 分离，并具有优异的非对映选择性 ( E / Z >20:1)。此外，我们还展示了代表性烯丙酯的新型 LDA 引发、TMSCl 介导的爱尔兰-克莱森重排。