4-((1S,2R)-3,3-dimethyl-2-(3-oxobutyl)cyclobutyl)pent-4-enoic acid

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 4-((1S,2R)-3,3-dimethyl-2-(3-oxobutyl)cyclobutyl)pent-4-enoic acid
• 英文别名: caryophyllonic acid；4-[3,3-dimethyl-2-(3-oxobutyl)cyclobutyl]-pent-4-enoic acid；β-caryophyllonic acid；4-[(1S,2R)-3,3-dimethyl-2-(3-oxobutyl)cyclobutyl]pent-4-enoic acid
• 化学式: C₁₅H₂₄O₃
• 分子量: 252.354
• InChiKey: VGNFSHPHIKPNED-CHWSQXEVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-((1S,2R)-3,3-dimethyl-2-(3-oxobutyl)cyclobutyl)pent-4-enoic acid 在 Lindlar's catalyst mixture of ozone and oxygen (5.5percent masspercent of O₃) 、 氢气 、 氧气 、 臭氧 作用下， 生成 4-oxo-4-<3,3-dimethyl-trans-2-(3-oxobutyl)cyclobutyl>butyric acid
  参考文献：
  名称：

  Odinokov, V. N.; Kukovinets, O. S.; Isakova, L. A., Journal of Organic Chemistry USSR (English Translation), 1985, vol. 21, # 5, p. 901 - 905

  摘要：

  DOI：
• 作为产物：
  描述：

  4-((1S,2R)-3,3-dimethyl-2-(3-oxobutyl)cyclobutyl)pent-4-enal 在 sodium chlorite 、 sodium dihydrogenphosphate 、 2-甲基-2-丁烯 作用下， 以 水 、 叔丁醇 为溶剂， 反应 4.0h， 以75%的产率得到4-((1S,2R)-3,3-dimethyl-2-(3-oxobutyl)cyclobutyl)pent-4-enoic acid
  参考文献：
  名称：

  Rumphellaones AC 及其 C-8 差向异构体从 β-石竹烯的简洁仿生半合成。

  摘要：

  朝向rumphellaones B（第一半合成路线2）和C（3）和它们的C-8差向异构体以及rumphellaone A（最短合成1），并从最容易获得的倍半萜，β石竹其C-8差向异构体（4）， 被表达。合成路线涉及石竹酸作为关键中间体，通过酸催化内酯化将其转化为鹿鞭草酮 A（和差向异构体），并使用一锅环氧化 - 内酯化将鹿鞭草酮 C（和差向异构体）。Rumphellaone B ( 2 ) 及其差向异构体是从rumphellaone A ( 1) 及其差向异构体，分别使用 Saegusa-Ito 氧化。C-8 处的绝对构型通过对rumphellaone B ( 2 ) 和rumphellaone C 的酰化衍生物进行单晶X 射线分析证实。

  DOI：

  10.1021/acs.jnatprod.0c00403

文献信息

• The gas-phase ozonolysis of β-caryophyllene (C15H24). Part I: an experimental study
  作者：Richard Winterhalter、Frank Herrmann、Basem Kanawati、Thanh Lam Nguyen、Jozef Peeters、Luc Vereecken、Geert K. Moortgat

  DOI：10.1039/b817824k

  日期：——

  The gas phase reaction of ozone with β-caryophyllene was investigated in a static glass reactor at 750 Torr and 296 K under various experimental conditions. The reactants and gas phase products were monitored by FTIR-spectroscopy and proton-transfer-reaction mass spectrometry (PTR-MS). Aerosol formation was monitored with a scanning mobility particle sizer (SMPS) and particulate products analysed by liquid chromatography/mass spectrometry (HPLC-MS). The different reactivity of the two double bonds in β-caryophyllene was probed by experiments with different ratios of reactants. An average rate coefficient at 295 K for the first-generation products was determined as 1.1 × 10−16 cm3 molecule−1 s−1. Using cyclohexane as scavenger, an OH-radical yield of (10.4 ± 2.3)% was determined for the ozonolysis of the more reactive internal double bond, whereas the average OH-radical yield for the ozonolysis of the first-generation products was found to be (16.4 ± 3.6)%. Measured gas phase products are CO, CO2 and HCHO with average yields of (2.0 ± 1.8)%, (3.8 ± 2.8)% and (7.7 ± 4.0)%, respectively for the more reactive internal double bond and (5.5 ± 4.8)%, (8.2 ± 2.8)% and (60 ± 6)%, respectively from ozonolysis of the less reactive double bond of the first-generation products. The residual FTIR spectra indicate the formation of an internal secondary ozonide of β-caryophyllene. From experiments using HCOOH as a Criegee intermediate (CI) scavenger, it was concluded that at least 60% of the formed CI are collisionally stabilized. The aerosol yield in the ozonolysis of β-caryophyllene was estimated from the measured particle size distributions. In the absence of a CI scavenger the yield ranged between 5 and 24%, depending on the aerosol mass. The yield increases with addition of water vapour or with higher concentrations of formic acid. In the presence of HCHO, lower aerosol yields were observed. This suggests that HCOOH adds to a Criegee intermediate to form a low-volatility compound responsible for aerosol formation. The underlying reaction mechanisms are discussed and compared with the results from the accompanying theoretical paper.

  1.1 cm3/mol/s。
• Odinokov, V. N.; Kukovinets, O. S.; Isakova, L. A., Journal of Organic Chemistry USSR (English Translation), 1985, vol. 21, # 5, p. 901 - 905
  作者：Odinokov, V. N.、Kukovinets, O. S.、Isakova, L. A.、Zainullin, R. A.、Dubovenko, Zh. V.、Tolstikov, G. A.

  DOI：——

  日期：——
• A Concise Bioinspired Semisynthesis of Rumphellaones A–C and Their C-8 Epimers from β-Caryophyllene
  作者：Georgijs Stakanovs、Anatoly Mishnev、Dace Rasina、Aigars Jirgensons

  DOI：10.1021/acs.jnatprod.0c00403

  日期：2020.6.26

  their C-8 epimers as well as the shortest synthesis of rumphellaone A (1) and its C-8 epimer from the most accessible sesquiterpene, β-caryophyllene (4), is presented. Synthetic routes involved caryophyllonic acid as a key intermediate, which was converted to rumphellaone A (and epimer) via acid-catalyzed lactonization and rumphellaone C (and epimer) using one-pot epoxidation–lactonization. Rumphellaone

  朝向rumphellaones B（第一半合成路线2）和C（3）和它们的C-8差向异构体以及rumphellaone A（最短合成1），并从最容易获得的倍半萜，β石竹其C-8差向异构体（4）， 被表达。合成路线涉及石竹酸作为关键中间体，通过酸催化内酯化将其转化为鹿鞭草酮 A（和差向异构体），并使用一锅环氧化 - 内酯化将鹿鞭草酮 C（和差向异构体）。Rumphellaone B ( 2 ) 及其差向异构体是从rumphellaone A ( 1) 及其差向异构体，分别使用 Saegusa-Ito 氧化。C-8 处的绝对构型通过对rumphellaone B ( 2 ) 和rumphellaone C 的酰化衍生物进行单晶X 射线分析证实。