2-isopropyl-3-methoxy-5-methyl-1,4-benzoquinone | 78525-33-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-isopropyl-3-methoxy-5-methyl-1,4-benzoquinone
• 英文别名: 3-methoxythymoquinone；2-Isopropyl-3-methoxy-5-methylbenzo-1,4-quinone；3-methoxy-5-methyl-2-propan-2-ylcyclohexa-2,5-diene-1,4-dione
• CAS: 78525-33-4
• 化学式: C₁₁H₁₄O₃
• 分子量: 194.23
• InChiKey: IZFIBRMTHIYADJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,3-丁二烯 、 2-isopropyl-3-methoxy-5-methyl-1,4-benzoquinone 在 chiral oxazaborolidinium*Tf₂N^(1-) derivative 作用下， 以 甲苯 为溶剂， 以99%的产率得到(+)-(4aR,8aS)-4a,5,8,8a-tetrahydro-2-isopropyl-3-methoxy-4a-methylnaphthalene-1,4-dione
  参考文献：
  名称：

  Application of Chiral Cationic Catalysts to Several Classical Syntheses of Racemic Natural Products Transforms Them into Highly Enantioselective Pathways

  摘要：

  This paper describes the application of chiral oxazaborolidinium cations of type 2 to various enantioselective Diels-Alder reactions that have served as early key steps for the syntheses of complex natural products. In the original syntheses these Diels-Alder reactions produced racemic adducts and led to racemic target molecules unless a separation of enantiomers by classical resolution was employed. By use of chiral catalysts of type 2, chiral products were obtained directly from Diels-Alder reactions of achiral components in excellent yield and enantioselectivity and with the mechanistically predicted absolute configuration. As a result, a number of classical syntheses could be converted to enantioselective versions, including (1) cortisone/cortisol (Merck/Sarett), (2) dendrobine (Kende), (3) vitamin B-12 (Eschenmoser), (4) myrocin C (Chu-Moyer/Danishefsky), (5) coriolin and hirsutene (Mehta), (6) dendrobatid 251F (Aube), (7) silphinene (Ito), and (8) nicandrenone core (Stoltz/Corey).

  DOI：

  10.1021/ja046154m
• 作为产物：
  描述：

  1,3-二甲氧基-4-羟基-2-异丙基苯 在 palladium 10% on activated carbon 、 氢气 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 sodium hydroxide 作用下， 以 甲醇 、 硝基甲烷 、 水 为溶剂， 反应 37.0h， 生成 2-isopropyl-3-methoxy-5-methyl-1,4-benzoquinone
  参考文献：
  名称：

  Efficient Generation of ortho-Quinone Methide: Application to the Biomimetic Syntheses of (±)-Schefflone and Tocopherol Trimers

  摘要：

  An efficient method using silver oxide-mediated oxidation for the synthesis of ortho-quinone methides has been developed and applied to the biomimetic syntheses of novel trimeric natural products, (+/-)-schefflone and tocopherol trimers. Further studies of the critical trimerization as well as substrate scope and limitations are also reported.

  DOI：

  10.1021/ol202641y

文献信息

• Short, Enantioselective Total Synthesis of Aflatoxin B₂ Using an Asymmetric [3+2]-Cycloaddition Step
  作者：Gang Zhou、E. J. Corey

  DOI：10.1021/ja054503m

  日期：2005.8.1

  A highly enantioselective [3+2]-cycloaddition reaction of 2,3-dihydrofuran with 1,4-benzoquinones using a chiral oxazaborolidinium triflimidate as catalyst has been developed which allows rapid access to a variety of chiral phenolic tricycles (enantiomeric excesses ranging from 91 to 98%). The utility of this new methodology is demonstrated by a short synthesis of the important pentacyclic natural

  使用手性 oxazaborolidinium trifliimidate 作为催化剂，2,3-二氢呋喃与 1,4-苯醌的高度对映选择性 [3+2]-环加成反应已被开发，该反应可以快速获得各种手性酚类三环（对映体过量范围为 91到 98%）。重要的五环天然产物黄曲霉毒素 B2 的短合成证明了这种新方法的实用性。这项探索性研究表明，这些催化剂可能更广泛地应用于对映选择性环加成。
• Carbon-13 NMR studies of benzoquinones
  作者：P. Joseph-Nathan、D. Abramo-Bruno、D. A. Ortega

  DOI：10.1002/mrc.1270150321

  日期：1981.3

  AbstractThe assignment of all ring carbons of p‐benzoquinones derived from perezone and from thymoquinone was completed using gated decoupled spectra. The long range proton‐carbon couplings are discussed in terms of the degree of substitution of the quinone ring. The tautomeric interconversion of the two energetically equivalent forms of 2,5‐dihydroxy‐1,4‐benzoquinones has been studied in various solvents and at several temperatures.
• Efficient Generation of <i>ortho</i>-Quinone Methide: Application to the Biomimetic Syntheses of (±)-Schefflone and Tocopherol Trimers
  作者：Daohong Liao、Houhua Li、Xiaoguang Lei

  DOI：10.1021/ol202641y

  日期：2012.1.6

  An efficient method using silver oxide-mediated oxidation for the synthesis of ortho-quinone methides has been developed and applied to the biomimetic syntheses of novel trimeric natural products, (+/-)-schefflone and tocopherol trimers. Further studies of the critical trimerization as well as substrate scope and limitations are also reported.
• Application of Chiral Cationic Catalysts to Several Classical Syntheses of Racemic Natural Products Transforms Them into Highly Enantioselective Pathways
  作者：Qi-Ying Hu、Gang Zhou、E. J. Corey

  DOI：10.1021/ja046154m

  日期：2004.10.1

  This paper describes the application of chiral oxazaborolidinium cations of type 2 to various enantioselective Diels-Alder reactions that have served as early key steps for the syntheses of complex natural products. In the original syntheses these Diels-Alder reactions produced racemic adducts and led to racemic target molecules unless a separation of enantiomers by classical resolution was employed. By use of chiral catalysts of type 2, chiral products were obtained directly from Diels-Alder reactions of achiral components in excellent yield and enantioselectivity and with the mechanistically predicted absolute configuration. As a result, a number of classical syntheses could be converted to enantioselective versions, including (1) cortisone/cortisol (Merck/Sarett), (2) dendrobine (Kende), (3) vitamin B-12 (Eschenmoser), (4) myrocin C (Chu-Moyer/Danishefsky), (5) coriolin and hirsutene (Mehta), (6) dendrobatid 251F (Aube), (7) silphinene (Ito), and (8) nicandrenone core (Stoltz/Corey).

表征谱图