methyl 3-isopropyl-7a-methyl-5-oxo-2,3-dihydro-7aH-pyrrolo<2,1-b>oxazole-6-carboxylate | 116910-12-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧氮杂卓类
• 英文名称: methyl 3-isopropyl-7a-methyl-5-oxo-2,3-dihydro-7aH-pyrrolo<2,1-b>oxazole-6-carboxylate
• 英文别名: methyl 3-isopropyl-7a-methyl-5-oxo-2,3-dihydro-7aH-pyrrolo[2,1-b]oxazole-6-carboxylate；methyl (3S,7aR)-7a-methyl-5-oxo-3-propan-2-yl-2,3-dihydropyrrolo[2,1-b][1,3]oxazole-6-carboxylate
• CAS: 116910-12-4
• 化学式: C₁₂H₁₇NO₄
• 分子量: 239.271
• InChiKey: PJEURVCXMFQVDE-BXKDBHETSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 3-isopropyl-7a-methyl-5-oxo-2,3-dihydro-7aH-pyrrolo<2,1-b>oxazole-6-carboxylate 在 硫酸 作用下， 以 甲醇 为溶剂， 反应 96.0h， 生成 <2S>-2-Isopropenylcyclopropan-1,1-dicarbonsaeure-dimethylester
  参考文献：
  名称：

  A novel asymmetric synthesis of substituted cyclopropanes

  摘要：

  DOI：

  10.1021/ja00229a067
• 作为产物：
  描述：

  生成 methyl 3-isopropyl-7a-methyl-5-oxo-2,3-dihydro-7aH-pyrrolo<2,1-b>oxazole-6-carboxylate
  参考文献：
  名称：

  手性双环内酰胺的非对映选择性环丙烷化产生对映体纯的环丙烷。在CIS-（1S，3R）-溴甲亚甲基酸和R-（-）-双蝶呤C的全合成中的应用

  摘要：

  基于容易获得的手性双环内酰胺（1b-c，6a-b）的新型非对映选择性环丙烷化提供了许多对映体纯的环丙烷。不饱和内酰胺类（的Cyclopropanations 10A-H ，12-14使用硫叶立德以及一个3 + 2环加成光解序列进行），并得到所需环丙烷加合物（16，17，19，22），以中等至极高的收益率。在所有涉及硫叶立德的情况下，环丙烷化反应都具有很高的exo / endo非对映选择性（>; 90％）。然而，发现外型与内型的加成模式高度依赖于不饱和内酰胺的角取代基。在重氮烷环加成的情况下，在所有情况下均观察到高区域选择性，尽管外/内选择性由所用重氮烷决定。重氮异丙烷比重氮甲烷更具反应性，通常导致较低的非对映异构体比率。次要非对映体可以通过色谱法或在多数情况下容易地除去由单个重结晶，提供非对映体纯的环丙基双环内酰胺（16，17，19，22）。该方法在生物学上具有重要意义的化合物的应用以高对

  DOI：

  10.1016/s0040-4020(01)85604-0

文献信息

• Non-metallocatalyzed epoxidation of chiral unsaturated lactams by tertiary amine N-oxides
  作者：C.J. Andres、N. Spetseris、J.R. Norton、A.I. Meyers

  DOI：10.1016/0040-4039(95)00114-r

  日期：1995.3

  Tertiary amine N-oxides were used to stereospecifically epoxidize chiral unsaturated bicyclic lactams in high yields (90–99%) at room temperature. This appears to be the first reported example of tertiary amine N-oxides acting as epoxidizing agents in the absence of a metal catalyst.

  叔胺N-氧化物用于在室温下以高产率（90-99％）立体定向环氧化手性不饱和双环内酰胺。这似乎是在没有金属催化剂的情况下叔胺N-氧化物起环氧化剂作用的第一个报道实例。
• Single and Double Diastereoselection in Azomethine Ylide Cycloaddition Reactions with Unsaturated Chiral Bicyclic Lactams
  作者：Andrew H. Fray、A. I. Meyers

  DOI：10.1021/jo9600870

  日期：1996.1.1

  Double diastereoselectivity data were analyzed to provide insight into the structural features that influence pi-facial selectivity in 1,3-dipolar cycloadditions of chiral and achiral azomethine ylides to chiral, unsaturated bicyclic lactams. Three major steric contributions to the differences in stability (Delta Delta G(double dagger)) between competing cycloaddition transition states were identified. The first major set of steric interactions involve that between the dipoles and the substituents on the left hemisphere (R(2)) and concave faces of the bicyclic lactams. This effectively hindered both alpha- and beta-approaches in the nonextended transition states shown in Figure 1. The second major steric interaction was provided by the nonbonded interactions (i) between the R(1) angular substituent on the bicyclic lactam and the pi-system of the dipole as shown in Figures 3 and 4. This interaction was shown to be very significant, causing reversal in pi-facial attack of chiral and achiral dipoles when the angular substituent is changed from phenyl or methyl to hydrogen. The high diastereoselectivity observed now opens a route to highly substituted chiral, nonracemic pyrrolidines.
• Diastereoselective azomethine ylide cycloadditions to unsaturated, chiral bicyclic lactams
  作者：Andrew H. Fray、A.I. Meyers

  DOI：10.1016/s0040-4039(00)92506-1

  日期：1992.6

  The levels of diastereoselection resulting from the 1,3-dipolar cycloaddition of chiral and achiral azomethine ylides 2(a-c) to chiral, unsaturated bicyclic lactams 1(a-f) are described in terms of steric factors.
• An asymmetric route to enantiomerically pure 1,2,3-trisubstituted cyclopropanes
  作者：Daniel Romo、A. I. Meyers

  DOI：10.1021/jo00049a038

  日期：1992.11

  Cycloaddition of various sulfur ylides to the chiral unsaturated lactams 1a, 1b led to cyclopropanated products containing a monosubstituted appendage. The stereochemical outcome is such that all the products are mainly (or exclusively) the kinetically controlled endo-syn-8, -9, or endo-anti-10. The latter occurs by virtue of an epimerization to the thermodynamically favored product. Removal of the chiral auxiliary following Wittig reaction on the intermediate carbinol amines (11, 15) gave chiral, nonracemic 1,2,3-trisubstituted cyclopropanes containing various functionalities (13, 16).
• Asymmetric Diels-Alder reactions of chiral α,β-unsaturated lactams
  作者：A.I. Meyers、Carl A. Busacca

  DOI：10.1016/s0040-4039(01)93401-x

  日期：——