3-(4,4-Dimethyl-5-oxo-tetrahydro-furan-2-yl)-propionitrile | 104223-02-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: 3-(4,4-Dimethyl-5-oxo-tetrahydro-furan-2-yl)-propionitrile
• CAS: 104223-02-1
• 化学式: C₉H₁₃NO₂
• 分子量: 167.208
• InChiKey: UMOYDOZXCLEWBY-UHFFFAOYSA-N

物化性质

• 沸点：
  333.9±15.0 °C(Predicted)
• 密度：
  1.031±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.63
• 重原子数：
  12.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  50.09
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  2,2-二甲基-4-戊酸甲酯 在 过氧化苯甲酰 吡啶 作用下， 以 正戊烷 为溶剂， 反应 24.0h， 生成 3-(4,4-Dimethyl-5-oxo-tetrahydro-furan-2-yl)-propionitrile
  参考文献：
  名称：

  分子内均质置换7 —不饱和过氧化合物的自由基加成：氧化杂环的合成

  摘要：

  将氢供体溶剂自由基加到过戊-4-烯酸叔丁酯中，得到4-取代的γ-丁内酯，产率为50％或更高。应用于烯丙基叔丁基过氧化物的这种反应已经产生了这些溶剂的2，3-环氧丙烷化。4-甲基-过戊-4-烯酸酯叔丁基，2,2-二甲基-过戊-4-烯酸酯叔丁基和过氧化甲基叔丁基甲基烯丙基也发生了类似的加成消除过程，但对于叔丁基5则失败了。 -甲基-己基-4-烯酸酯和叔丁基-3-甲基-丁-2-烯基过氧化物。

  DOI：

  10.1016/s0040-4020(01)97183-2

文献信息

• tert‐Butyl as a Functional Group: Non‐Directed Catalytic Hydroxylation of Sterically Congested Primary C−H Bonds
  作者：Siu‐Chung Chan、Andrea Palone、Massimo Bietti、Miquel Costas

  DOI：10.1002/anie.202402858

  日期：2024.7.8

  The tert‐butyl group is a common aliphatic motif extensively employed to implement steric congestion and conformational rigidity in organic and organometallic molecules. Because of the combination of a high bond dissociation energy (~100 kcal mol−1) and limited accessibility, in the absence of directing groups, neither radical nor organometallic approaches are effective for the chemical modification of tert‐butyl C−H bonds. Herein we overcome these limits by employing a highly electrophilic manganese catalyst, [Mn(CF3bpeb)(OTf)2], that operates in the strong hydrogen bond donor solvent nonafluoro‐tert‐butyl alcohol (NFTBA) and catalytically activates hydrogen peroxide to generate a powerful manganese‐oxo species that effectively oxidizes tert‐butyl C−H bonds. Leveraging on the interplay of steric, electronic, medium and torsional effects, site‐selective and product chemoselective hydroxylation of the tert‐butyl group is accomplished with broad reaction scope, delivering primary alcohols as largely dominant products in preparative yields. Late‐stage hydroxylation at tert‐butyl sites is demonstrated on 6 densely functionalized molecules of pharmaceutical interest. This work uncovers a novel disconnection approach, harnessing tert‐butyl as a potential functional group in strategic synthetic planning for complex molecular architectures.