N-methyl-N-methoxy-2-[(3-phenylprop-2-yn-1-yl)oxy]acetamide | 923026-24-8

• 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: N-methyl-N-methoxy-2-[(3-phenylprop-2-yn-1-yl)oxy]acetamide
• 英文别名: N-methoxy-N-methyl-2-((3-phenylprop-2-yn-1-yl)oxy)acetamide；N-Methoxy-N-methyl-2-[(3-phenylprop-2-yn-1-yl)oxy]acetamide；N-methoxy-N-methyl-2-(3-phenylprop-2-ynoxy)acetamide
• CAS: 923026-24-8
• 化学式: C₁₃H₁₅NO₃
• 分子量: 233.267
• InChiKey: AJEFKIYJDLUJFA-UHFFFAOYSA-N

物化性质

• 沸点：
  327.4±52.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-methyl-N-methoxy-2-[(3-phenylprop-2-yn-1-yl)oxy]acetamide 在 hexaaquonickel(II) bis(p-toluenesulfonate) 、 甲基二乙氧基硅烷 、 (3aS,8aR)-2-(2-diphenylphosphinophenyl)-3a,8a-dihydroindane[1,2-d]oxazole 作用下， 以 四氢呋喃 、 乙二醇二甲醚 为溶剂， 反应 23.0h， 生成 (S)-3-(2-methylprop-1-en-1-yl)-4-phenyl-3,6-dihydro-2H-pyran-3-ol
  参考文献：
  名称：

  Precatalyst‐Enabled Selectivity: Enantioselective NiH‐Catalyzed anti ‐Hydrometalative Cyclization of Alkynones to Endo ‐ and Heterocyclic Allylic Alcohols

  摘要：

  AbstractA highly enantioselective NiH‐catalyzed hydrocyclization of alkynones with unparalleled anti‐ and endocyclic selectivities is described. The choice of the precatalysts has significant influence in tuning the regio‐ and enantioselectivity. Using Ni(OTs)2/Phox as a precatalyst and (EtO)2MeSiH as a hydride source, an array of enantioenriched O‐, N‐, and S‐containing heterocyclic tertiary allylic alcohols are obtained in 24–81 % yields with 80:20–99:1 er. Mechanistic investigations and synthetic application are also carried out. This study represents an efficient access to a set of allylic alcohols that are unable to access by the state‐of‐the‐art coupling reactions.

  DOI：

  10.1002/anie.202110815
• 作为产物：
  描述：

  ethyl [(3-phenylprop-2-yn-1-yl)oxy]acetate 在 氢氧化钾 、 O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate 、 N,N-二异丙基乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 N-methyl-N-methoxy-2-[(3-phenylprop-2-yn-1-yl)oxy]acetamide
  参考文献：
  名称：

  光-脱氢-狄尔斯-阿尔德反应合成苯并[ g ]异色酮

  摘要：

  事实证明，光脱氢-狄尔斯-阿尔德（PDDA）反应是制备高官能度萘的通用方法。因此，酮1可以环化成1 H-苯并[ g ]异色n-4-（3 H）-酮11和12，大部分收率很高。研究了各种取代基对反应区域选择性的影响，并在理论计算的基础上探讨了机理。

  DOI：

  10.1002/hlca.200690241

文献信息

• Highly Enantioselective Nickel-Catalyzed Intramolecular Reductive Cyclization of Alkynones
  作者：Wenzhen Fu、Ming Nie、Aizhen Wang、Ziping Cao、Wenjun Tang

  DOI：10.1002/anie.201410700

  日期：2015.2.16

  The first asymmetric nickel‐catalyzed intramolecular reductive cyclization of alkynones is reported. A P‐chiral monophosphine and triethylsilane were used as the ligand and the reducing reagent, respectively, to form a series of tertiary allylic alcohols bearing furan/pyran rings in excellent yields and enantioselectivities. This reaction has a broad substrate scope and enabled the efficient synthesis

  报道了炔烃的第一个不对称镍催化的分子内还原环化反应。AP-手性单膦和三乙基硅烷分别用作配体和还原剂，以优异的收率和对映选择性形成一系列带有呋喃/吡喃环的叔烯丙基醇。该反应具有广泛的底物范围，并能够有效地合成脱羟基立方体蛋白和手性二苯并环辛二烯骨架。
• The Photo-Dehydro-Diels-Alder (PDDA) Reaction - A Powerful Method for the Preparation of Biaryls
  作者：Pablo Wessig、Gunnar Müller、Charlotte Pick、Annika Matthes

  DOI：10.1055/s-2006-958949

  日期：2007.2

  The photochemically initiated dehydro-Diels-Alder (PDDA) reaction is an efficient and versatile method for the prepa- ration of biaryls. The ring closure may take place both inter- and in- tramolecularly, of which the intramolecular variant is more productive from the preparative point of view. A variety of linkers can be employed to connect the ynone moiety, which acts as the chromophore, with another

  光化学引发的脱氢-狄尔斯-阿尔德 (PDDA) 反应是制备联芳基化合物的一种有效且通用的方法。闭环可以发生在分子间和分子内，从制备的角度来看，分子内变体的生产效率更高。可以使用多种接头将充当发色团的ynone部分与另一个乙炔基团连接起来，从而实现大的结构多功能性。此处还将讨论影响 PDDA 反应位点选择性的原理。
• Precatalyst‐Enabled Selectivity: Enantioselective NiH‐Catalyzed <i>anti</i> ‐Hydrometalative Cyclization of Alkynones to <i>Endo</i> ‐ and Heterocyclic Allylic Alcohols
  作者：Xiao‐Wen Zhang、Ming‐Hui Zhu、Hai‐Xiang Zeng、Qi‐Yang Li、Wen‐Bo Liu

  DOI：10.1002/anie.202110815

  日期：2021.12.20

  AbstractA highly enantioselective NiH‐catalyzed hydrocyclization of alkynones with unparalleled anti‐ and endocyclic selectivities is described. The choice of the precatalysts has significant influence in tuning the regio‐ and enantioselectivity. Using Ni(OTs)2/Phox as a precatalyst and (EtO)2MeSiH as a hydride source, an array of enantioenriched O‐, N‐, and S‐containing heterocyclic tertiary allylic alcohols are obtained in 24–81 % yields with 80:20–99:1 er. Mechanistic investigations and synthetic application are also carried out. This study represents an efficient access to a set of allylic alcohols that are unable to access by the state‐of‐the‐art coupling reactions.
• Synthesis of Benzo[g]isochromenes through Photo-Dehydro-Diels–Alder Reaction
  作者：Pablo Wessig、Gunnar Müller、Robert Herre、Andreas Kühn

  DOI：10.1002/hlca.200690241

  日期：2006.11

  The Photo-Dehydro-Diels–Alder (PDDA) reaction is shown to be a versatile method for the preparation of highly functionalized naphthalenes. Thus, ketones 1 could be cyclized to the 1H-benzo[g]isochromen-4-(3H)-ones 11 and 12, mostly in good yields. The influence of various substituents on the regioselectivity of the reaction was investigated, and the mechanism is discussed based on theoretical calculations

  事实证明，光脱氢-狄尔斯-阿尔德（PDDA）反应是制备高官能度萘的通用方法。因此，酮1可以环化成1 H-苯并[ g ]异色n-4-（3 H）-酮11和12，大部分收率很高。研究了各种取代基对反应区域选择性的影响，并在理论计算的基础上探讨了机理。