(2aS,4aR,8R)-2,2,4a,8-tetramethyl-2a,3,4,5,6,7-hexahydro-1H-cyclobuta[i]inden-8-ol | 80374-27-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (2aS,4aR,8R)-2,2,4a,8-tetramethyl-2a,3,4,5,6,7-hexahydro-1H-cyclobuta[i]inden-8-ol
• 英文别名: panasinsanol A；(2aS,4aR,8R,8aS)-2,2,4a,,8-tetramethyldecahydrocyclobutinden-8-ol
• CAS: 80374-27-2
• 化学式: C₁₅H₂₆O
• 分子量: 222.37
• InChiKey: ZEQZCZRDJPTCHI-MYPMTAMASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (2aS,4aR,8R)-2,2,4a,8-tetramethyl-2a,3,4,5,6,7-hexahydro-1H-cyclobuta[i]inden-8-ol 在 吡啶 、 氯化亚砜 作用下， 反应 0.17h， 以28%的产率得到(2aS,4aR,8aR)-2,2,4A-三甲基-8-亚甲基十氢环丁[c]茚
  参考文献：
  名称：

  Rearrangement of (-)-.beta.-Caryophyllene. A Product Analysis and Force Field Study

  摘要：

  The rearrangement of (-)-beta-caryophyllene (1) with sulfuric acid in ether has been reinvestigated. In the early stage, a multitude of products is formed. Of these, fourteen hydrocarbons (3, 4, 6-17) and four alcohols (5, 18-20) were obtained pure. From the very beginning, the tricycloundecenes 15-17 accumulate quickly. This indicates that a previously unknown rearrangement of 1 by protonation of the exocyclic double bond followed by transannular ring closure is a main reaction, and that the conformation beta alpha is involved. Three hydrocarbons (3, 4, 8) and three alcohols (5, 18, 19) proved to be stable. They are the main components in the late stage. A complete rearrangement scheme followed from a force field analysis using MMP2. First, all conformations up to 4 kcal above the global minimum of each product and each carbenium ion necessary for its formation were detected automatically using the search program HUNTER. Second, the conformation favoring a specific transformation was searched for. For transannular cyclizations, the conformation with the shortest distance between the atoms to be bound and, for ring openings and 1,2-shifts, the conformation with the smallest dihedral angle between the empty p-orbital and the bond to be broken were selected. In all cases, the selection criteria proved valid: The stereochemistry of the conformations selected matched the stereochemistry of the products observed. On the basis of the results presented, a fully automated search prog ram for favorable rearrangement paths may be developed.

  DOI：

  10.1021/ja00141a009
• 作为产物：
  描述：

  2-Hydroxymethyl-3-methyl-3-(4-methyl-pent-3-enyl)-cyclohexanone 在 吡啶 、 potassium tert-butylate 、 镍 作用下， 以 四氢呋喃 、 叔丁醇 、 正戊烷 为溶剂， 反应 185.0h， 生成 (2aS,4aR,8R)-2,2,4a,8-tetramethyl-2a,3,4,5,6,7-hexahydro-1H-cyclobuta[i]inden-8-ol
  参考文献：
  名称：

  Ketone methylenation with optical resolution. Total synthesis of the ginseng sesquiterpene (-)-.beta.-panasinsene and its enantiomer

  摘要：

  DOI：

  10.1021/ja00415a052

文献信息

• Studies on the sesquiterpenoids of Panax ginseng C.A. Meyer. Isolation and structure determination of sesquiterpene alcohols, panasinsanols A and B.
  作者：HISAKATSU IWABUCHI、MASAHIRO YOSHIKURA、YOSHITOMI IKAWA、WASUKE KAMISAKO

  DOI：10.1248/cpb.35.1975

  日期：——

  Two sesquiterpene alcohols, panasinsanol A (1) and panasinsanol B (2), were isolated from the rootlets of Panax ginseng C. A. MEYER (Araliaceae) together with known sesquiterpene hydro-carbons, α-panasinsene (3), β-panasinsene (4), α-neoclovene (5), and β-neoclovene (6). The structures of 1 and 2 were established by spectral evidence, chemical correlations to congener hydrocarbons (3, 4, 5, and 6), and finally by their syntheses from (-) -β-caryophyllene. This is the first isolation of 1 from a natural source, and 2 is a novel panasinsane-type sesquiterpene.

  从人参（Araliaceae）的根茎中分离出两种倍半萜醇，即panasinsanol A（1）和panasinsanol B（2），以及已知的倍半萜烃，即α-panasinsene（3）、β-panasinsene（4）、α-neoclovene（5）和β-neoclovene（6）。1和2的结构通过光谱证据、与同系烃（3、4、5和6）的化学相关性，以及最终通过从（-）-β-石竹烯合成来确定。这是首次从天然来源分离出1，而2是一种新型的panasinsane型倍半萜。
• Rearrangement of (-)-.beta.-Caryophyllene. A Product Analysis and Force Field Study
  作者：Lutz Fitjer、Andreas Malich、Carola Paschke、Sabine Kluge、Ralf Gerke、Beate Rissom、Joerg Weiser、Mathias Noltemeyer

  DOI：10.1021/ja00141a009

  日期：1995.9

  The rearrangement of (-)-beta-caryophyllene (1) with sulfuric acid in ether has been reinvestigated. In the early stage, a multitude of products is formed. Of these, fourteen hydrocarbons (3, 4, 6-17) and four alcohols (5, 18-20) were obtained pure. From the very beginning, the tricycloundecenes 15-17 accumulate quickly. This indicates that a previously unknown rearrangement of 1 by protonation of the exocyclic double bond followed by transannular ring closure is a main reaction, and that the conformation beta alpha is involved. Three hydrocarbons (3, 4, 8) and three alcohols (5, 18, 19) proved to be stable. They are the main components in the late stage. A complete rearrangement scheme followed from a force field analysis using MMP2. First, all conformations up to 4 kcal above the global minimum of each product and each carbenium ion necessary for its formation were detected automatically using the search program HUNTER. Second, the conformation favoring a specific transformation was searched for. For transannular cyclizations, the conformation with the shortest distance between the atoms to be bound and, for ring openings and 1,2-shifts, the conformation with the smallest dihedral angle between the empty p-orbital and the bond to be broken were selected. In all cases, the selection criteria proved valid: The stereochemistry of the conformations selected matched the stereochemistry of the products observed. On the basis of the results presented, a fully automated search prog ram for favorable rearrangement paths may be developed.
• Ketone methylenation with optical resolution. Total synthesis of the ginseng sesquiterpene (-)-.beta.-panasinsene and its enantiomer
  作者：Carl R. Johnson、Nicholas A. Meanwell

  DOI：10.1021/ja00415a052

  日期：1981.12