acetic acid-(2,2,3,3-tetramethyl-butyl ester) | 99850-70-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: acetic acid-(2,2,3,3-tetramethyl-butyl ester)
• 英文别名: Essigsaeure-(2,2,3,3-tetramethyl-butylester)；2,2,3,3-Tetramethylbutyl acetate
• CAS: 99850-70-1
• 化学式: C₁₀H₂₀O₂
• 分子量: 172.268
• InChiKey: UEMSAWYTRZUCKJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  acetic acid-(2,2,3,3-tetramethyl-butyl ester) 在 双氧水 、 C₄₆H₄₀F₁₈MnN₆O₆S₂ 、 尿素 作用下， 以2 %的产率得到
  参考文献：
  名称：

  10.1002/anie.202402858

  摘要：

  AbstractThe 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.

  DOI：

  10.1002/anie.202402858
• 作为产物：
  描述：

  六甲基乙烷 在 四氯化碳 、 乙醚 、 氧气 、 氯 、 magnesium 作用下， 生成 acetic acid-(2,2,3,3-tetramethyl-butyl ester)
  参考文献：
  名称：

  Whitmore; Marker; Plambeck, Journal of the American Chemical Society, 1941, vol. 63, p. 1628

  摘要：

  DOI：

文献信息

• NOVEL CYCLOSPORIN DERIVATIVES AND USES THEREOF
  申请人：S&T Global Inc.

  公开号：US20190151403A1

  公开（公告）日：2019-05-23

  A compound of the Formula (I) is disclosed: (I) or pharmaceutically acceptable salt thereof, wherein the symbols are as defined in the specification. Also described are a pharmaceutical composition comprising the same and a method for treating or preventing viral infections, inflammation, dry eye, central nervous disorders, cardiovascular diseases, cancer, obesity, diabetes, muscular dystrophy, lung, and liver, and kindey diseases, and hair loss using the same.
• Whitmore; Marker; Plambeck, Journal of the American Chemical Society, 1941, vol. 63, p. 1628
  作者：Whitmore、Marker、Plambeck

  DOI：——

  日期：——
• 10.1002/anie.202402858
  作者：Chan, Siu-Chung、Palone, Andrea、Bietti, Massimo、Costas, Miquel

  DOI：10.1002/anie.202402858

  日期：——

  AbstractThe 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.