4-(2-phenylethyl)-3,3,4-trimethyloxetan-2-one | 131436-04-9

• 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: 4-(2-phenylethyl)-3,3,4-trimethyloxetan-2-one
• 英文别名: 2,2,3-trimethyl-5-phenylpentan-3-olide；3,3,4-Trimethyl-4-(2-phenylethyl)oxetan-2-one
• CAS: 131436-04-9
• 化学式: C₁₄H₁₈O₂
• 分子量: 218.296
• InChiKey: GJTKYBZMPBQDSJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  4-(2-phenylethyl)-3,3,4-trimethyloxetan-2-one 在 silica gel 作用下， 以 环己烷 为溶剂， 反应 0.75h， 以95%的产率得到(3,4-dimethylpent-3-en-1-yl)benzene
  参考文献：
  名称：

  A practical and efficient method for the synthesis of .beta.-lactones

  摘要：

  This paper describes a convenient one-step preparation of beta-lactones based on the addition of thiol ester enolates to carbonyl compounds. Under the proper conditions the resulting aldolates undergo spontaneous cyclization to produce beta-lactones in good to excellent yield. The new beta-lactone synthesis provides access to 2-oxetanones with a variety of substituents and substitution patterns. In general, thiol ester enolates combine with carbonyl compounds to form the less sterically crowded beta-lactone diastereomers, and in some cases the reaction proceeds with excellent stereoselectivity. In conjunction with the stereospecific decarboxylation of beta-lactones, this chemistry also provides a very attractive approach to the synthesis of substituted alkenes.

  DOI：

  10.1021/jo00003a047
• 作为产物：
  描述：

  3-hydroxy-2,2,3-trimethyl-5-phenylpentanoic acid 在 4-二甲氨基吡啶 、 2-甲基-6-硝基苯甲酸酐 、 碳酸氢钠 、 三乙胺 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 12.0h， 以95%的产率得到4-(2-phenylethyl)-3,3,4-trimethyloxetan-2-one
  参考文献：
  名称：

  MNBA-Mediated β-Lactone Formation: Mechanistic Studies and Application for the Asymmetric Total Synthesis of Tetrahydrolipstatin

  摘要：

  Various beta-lactones were prepared from beta-hydroxycarboxylic acids by intramolecular dehydration condensation using MNBA, an effective coupling reagent, along with a nucleophilic catalyst. The transition state that provides the desired 4-membered ring model system is disclosed by density functional theory (DFT) calculations, and the structural features of the transition form are discussed. This method was successfully applied to the asymmetric total synthesis of tetrahydrolipstatin (THL), an antiobestic drug used in clinical treatment to inhibit the activity of pancreatic lipase.

  DOI：

  10.1021/jo300139r

文献信息

• Method for synthesizing .beta.-lactones and alkenes
  申请人：Massachusetts Institute of Technology

  公开号：US05004815A1

  公开（公告）日：1991-04-02

  .beta.-Lactones are synthesized from a thiol ester and a ketone by a method which efficiently produces .beta.-lactones in high yields. The method involves combining the thiol ester, a ketone or aldehyde, a base, and an organic solvent at subambient temperatures. The thiol ester and ketone form an adduct, which upon warming, spontaneously cyclizes to yield a .beta.-lactone. .beta.-Lactones formed by this method are then decarboxylated, generally by warming in the presence of an adsorbent in an organic solvent, to stereospecifically form the corresponding alkenes.

  .beta.-内酯是通过一种高产率的方法从硫酰酯和酮合成的。该方法涉及在亚环境温度下将硫酰酯、酮或醛、碱和有机溶剂结合在一起。硫酰酯和酮形成加合物，加热后自发环化形成.beta.-内酯。通过这种方法形成的.beta.-内酯通常通过在有机溶剂中加热存在吸附剂的情况下脱羧，以立体特异性形成相应的烯烃。
• [EN] METHOD FOR SYNTHESIZING beta -LACTONES AND ALKENES
  申请人：MASSACHUSETTS INSTITUTE OF TECHNOLOGY

  公开号：WO1990012792A1

  公开（公告）日：1990-11-01

  (EN) $g(b)-lactones are synthesized from a thiol ester and a ketone by a method which efficiently produces $g(b)-lactones in high yields. The method involves combining the thiol ester, ketone, or aldehyde base and organic solvent at subambient temperatures. The thiol ester and ketone form an adduct, which upon warming, spontaneously cyclizes to yield $g(b)-lactone. $g(b)-lactones formed by this method are then decarboxylated, generally by warming in the presence of an adsorbent in an organic solvent, to stereo-specifically form the corresponding alkenes.(FR) Des $g(b)-lactones sont synthétisés à partir d'un thiol ester et d'une cétone par un procédé qui permet de produire efficacement des $g(b)-lactones avec des pourcentages de production élevés. Le procédé consiste à combiner le thiol ester, la cétone ou la base aldéhide et le solvant organique à des températures inférieures à la température ambiante. Le thiol ester et la cétone forment un produit d'addition qui, en le chauffant, forme spontanément un anneau pour produire une $g(b)-lactone. Les $g(b)-lactones formées par ce procédé sont ensuite décarboxylées, en général en les chauffant en présence d'un adsorbant dans un solvant organique pour former de manière stéréospécifique les alcènes correspondants.

  $g(b)$-内酯通过一种高效且高产的方法合成，该方法利用硫氧酯和酮体（或醛基）通过一种在亚临界温度下进行的过程。具体来说，将硫氧酯、酮体或醛基与有机溶剂在低于室温的条件下混合，硫氧酯和酮体形成一个加成体，Upon加热，这个加成体会自发地进行环化反应生成$g(b)$-内酯。通过上述方法合成得到的$g(b)$-内酯随后进行去二氧化碳处理（通常在有机溶剂和吸附剂存在下加热），从而形成相应烯烃的形状选择性产物。
• DANHEISER, RICK L.;NOWICK, JAMES S., J. ORG. CHEM., 56,(1991) N, C. 1176-1185
  作者：DANHEISER, RICK L.、NOWICK, JAMES S.

  DOI：——

  日期：——
• US5004815A
  申请人：——

  公开号：US5004815A

  公开（公告）日：1991-04-02
• MNBA-Mediated β-Lactone Formation: Mechanistic Studies and Application for the Asymmetric Total Synthesis of Tetrahydrolipstatin
  作者：Isamu Shiina、Yuma Umezaki、Nobutaka Kuroda、Takashi Iizumi、Shunsuke Nagai、Takashi Katoh

  DOI：10.1021/jo300139r

  日期：2012.6.1

  Various beta-lactones were prepared from beta-hydroxycarboxylic acids by intramolecular dehydration condensation using MNBA, an effective coupling reagent, along with a nucleophilic catalyst. The transition state that provides the desired 4-membered ring model system is disclosed by density functional theory (DFT) calculations, and the structural features of the transition form are discussed. This method was successfully applied to the asymmetric total synthesis of tetrahydrolipstatin (THL), an antiobestic drug used in clinical treatment to inhibit the activity of pancreatic lipase.