(3S,7aR)-3-tert-butyl-7a-methyltetrahydropyrrolo[2,1-b]oxazol-5(6H)-one | 124062-47-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (3S,7aR)-3-tert-butyl-7a-methyltetrahydropyrrolo[2,1-b]oxazol-5(6H)-one
• 英文别名: (3S,7aR)-3-tert-butyl-7a-methyl-2,3,6,7-tetrahydropyrrolo[2,1-b][1,3]oxazol-5-one
• CAS: 124062-47-1
• 化学式: C₁₁H₁₉NO₂
• 分子量: 197.277
• InChiKey: NQLRBULCEPSHJH-LDYMZIIASA-N

物化性质

• 熔点：
  59-60 °C
• 沸点：
  291.9±19.0 °C(Predicted)
• 密度：
  1.07±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3S,7aR)-3-tert-butyl-7a-methyltetrahydropyrrolo[2,1-b]oxazol-5(6H)-one 生成 (3S,7aR)-3-tert-butyl-7a-methyl-2,3-dihydropyrrolo[2,1-b][1,3]oxazol-5-one
  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
• 作为产物：
  描述：

  L-叔亮氨醇 、 乙酰丙酸 以 甲苯 为溶剂， 反应 26.0h， 以95%的产率得到(3S,7aR)-3-tert-butyl-7a-methyltetrahydropyrrolo[2,1-b]oxazol-5(6H)-one
  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

• Chiral bicyclic lactams. An asymmetric synthesis of cis-(1s, 3r) deltamethrinic acid
  作者：A.I. Meyers、Daniel Romo

  DOI：10.1016/s0040-4039(00)99569-8

  日期：——

  Cyclopropanation of a chiral α,β-unsaturated bicyclic lactam derived from tert-leucinol and levulinic acid gave after 4 steps, the title compound in > 99% ee.

  衍生自叔亮氨酸和乙酰丙酸的手性α，β-不饱和双环内酰胺的环丙烷化经过4个步骤，得到标题化合物，其ee＞ 99％。
• An Asymmetric Approach to Spirocylic Systems:  A Formal Synthesis of Zizaene
  作者：Robert C. Hughes、Curt A. Dvorak、A. I. Meyers

  DOI：10.1021/jo010439p

  日期：2001.8.1

  A general route to enantiopure spirocarbocycles is described. The use of various chiral bicyclic lactams 1 that have been doubly alkylated with olefinic halides gives good yields of alpha,alpha -disubstituted chiral lactams 2 which were cyclized to spiro-olefins using ring closure metathesis methodology (Grubbs' catalyst). These spirolactams 3, formed in generally excellent yields, were shown to be smoothly transformed into spirocyclopentenone 6, spirocyclohexenone, 7, and spirolactams 8. Further demonstration of this spirocyclization methodology was featured in a formal synthesis of zizaene, by preparing in enantiomeric form the Coates' intermediate 21. This synthetic effort provided additional examples of the synthetic versatility of chiral bicyclic lactams 2a,b.
• 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.
• Synthesis of enantiomerically pure hydrinden-2-ones and benz[e]inden-2-ones via asymmetric alkylations of chiral bicyclic lactams
  作者：Lawrence Snyder、A. I. Meyers

  DOI：10.1021/jo00078a032

  日期：1993.12

  A route to the titled compounds in >99 % ee was achieved from sequential diastereoselective alkylations of chiral, nonracemic bicyclic lactams 6 and 15. An intramolecular addition of the organolithium species derived from 17a-c and 28a-d gave, after hydrolysis, diketones 25a-c and 30a-d, which were cyclized to the titled compounds 4a-c and 31a-d. As an example of the versatility of this method, the ABC ring system of the triterpene stelliferin A, isolated from marine organisms, was prepared in high enantiomeric excess.
• MEYERS, A. I.;ROMO, DANIEL, TETRAHEDRON LETT., 30,(1989) N4, C. 1745-1748
  作者：MEYERS, A. I.、ROMO, DANIEL

  DOI：——

  日期：——