2-((E)-3-(benzyloxy)prop-1-en-1-yl)-3-methyloxirane

• 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-((E)-3-(benzyloxy)prop-1-en-1-yl)-3-methyloxirane
• 英文别名: (2S,3S)-2-methyl-3-[(E)-3-phenylmethoxyprop-1-enyl]oxirane
• 化学式: C₁₃H₁₆O₂
• 分子量: 204.269
• InChiKey: HIMQOFHNLSDZGW-OBGXAZDVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  21.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-((E)-3-(benzyloxy)prop-1-en-1-yl)-3-methyloxirane 在 氨 、 对甲苯磺酸 作用下， 反应 72.0h， 以81%的产率得到(E,2R,3S)-3-amino-6-phenylmethoxyhex-4-en-2-ol
  参考文献：
  名称：

  Lindstroem, Ulf M.; Somfai, Peter, Synthesis, 1998, # 1, p. 109 - 117

  摘要：

  DOI：
• 作为产物：
  描述：

  (2E,4E)-2,4-己二烯-1-醇 在 sodium hydride 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 碳酸氢钠 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.5h， 生成 2-((E)-3-(benzyloxy)prop-1-en-1-yl)-3-methyloxirane
  参考文献：
  名称：

  乙烯基氮丙啶中的Aza- [3,3] -Claisen烯醇酸酯重排：单取代，二取代和三取代的七元内酰胺的立体选择性合成。

  摘要：

  几种2,3-二取代的乙烯基氮丙啶已被N-酰化，并在-78℃下于THF中进行LiHMDS处理。升温至室温后，所得酰胺烯酸酯进行高度立体选择性[3,3]-σ重排，得到单- ，二和三取代的七元内酰胺，收率高。通过使用各种取代的乙烯基氮丙啶已研究了该方法的范围和局限性。通过六元舟状过渡态组装进行的动力学控制过程已被用来解释反应的立体化学结果。

  DOI：

  10.1002/1521-3765(20010105)7:1<94::aid-chem94>3.0.co;2-m

文献信息

• Stereoselective Ring Expansion of Vinyl Oxiranes: Mechanistic Insights and Natural Product Total Synthesis
  作者：Matthew Brichacek、Lindsay A. Batory、Jon T. Njardarson

  DOI：10.1002/anie.200906830

  日期：2010.2.22

  applicable, catalytic, and stereoselective vinyl oxirane ring expansion is described (see scheme; hfacac=hexafluoroacetylacetonate). The stereoselectivity was influenced by several reaction parameters, and kinetic studies support a mechanistic proposal involving the in situ formation of a more reactive catalytic species. This ring‐expansion reaction has been employed in the asymmetric total synthesis

  真是（紧张）的解脱！描述了第一个广泛适用的，催化的和立体选择性的乙烯基环氧乙烷环扩环（参见方案； hfacac =六氟乙酰丙酮酸酯）。立体选择性受几个反应参数的影响，动力学研究支持了一种机制性的提议，涉及原位形成更具反应性的催化物质。该扩环反应已用于（+）-邻苯二酚二醇的不对称全合成中。
• The strategic marriage of method and motif. Total synthesis of varitriol
  作者：Matthew Brichacek、Lindsay A. Batory、Nicholas A. McGrath、Jon T. Njardarson

  DOI：10.1016/j.tet.2010.03.038

  日期：2010.6

  Detailed in this report are several new efficient synthetic approaches toward the natural product anti cancer agent varitriol, culminating in a concise total synthesis. A common theme for these routes is that they employ a new catalytic stereoselective vinyl oxirane ring expansion reaction, which provides rapid access to the common cis-2,5-tetrahydrofuran core. The combination of careful synthetic

  详述本报告中是几个新的有效的合成向天然产物接近抗癌剂varitriol，以简明的全合成最终。这些路线的共同主题是，它们采用了新的催化立体选择性乙烯基环氧乙烷环膨胀反应，该反应可快速进入常见的顺式-2,5-四氢呋喃核。仔细的合成设计和适当的起始材料选择相结合，使这种新方法（乙烯基环氧乙烷环扩环）与母题（varitriol）完美地结合在一起。
• Catalytic Regiodivergent Kinetic Resolution of Allylic Epoxides:  A New Entry to Allylic and Homoallylic Alcohols with High Optical Purity
  作者：Mauro Pineschi、Federica Del Moro、Paolo Crotti、Valeria Di Bussolo、Franco Macchia

  DOI：10.1021/jo035674h

  日期：2004.3.1

  A novel regiodivergent kinetic resolution of a series of allylic epoxides with alkylzinc reagents is described. Results demonstrate the potential of chiral copper-phosphoramidite catalysts for enantiomer differentiation of allylic epoxides, allowing a chiral catalyst-stereoregulated synthesis of cyclic allylic and homoallylic alcohols with high optical purities.
• A Regio- and Stereodivergent Route to All Isomers of <i>v</i><i>ic</i>-Amino Alcohols
  作者：Berit Olofsson、Peter Somfai

  DOI：10.1021/jo0262053

  日期：2002.11.1

  Vicinal amino alcohols are substructures in several important natural products. They are also frequently employed ligands in asymmetric synthesis. Many enantioselective syntheses of vic-amino alcohols have been reported, but each structure has required its own synthetic route. This study presents a synthetic strategy leading to all eight possible isomers of a given beta-amino alcohol, starting from vinyl epoxides. The developed strategy focuses on the propensity of vinyl epoxides and vinylaziridines to be selectively ring-opened at the allylic position by suitable hard nucleophiles. Within this strategy, a novel large-scale aminolysis reaction and the synthesis of a trisubstituted N-H vinylaziridine are detailed.