(-)-(1R,2R,4S)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane-6-ol | 103665-39-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (-)-(1R,2R,4S)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane-6-ol
• 英文别名: (-)-(1R,2R,4S)-2α-hydroxycineole；(1R)-6α-hydroxycineole；(-)-2-endo-hydroxy-1,8-cineole；endo-6-Hydroxycineol；2-Endo-hydroxy-1,8-cineole；(1R,4S,6R)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-6-ol
• CAS: 103665-39-0
• 化学式: C₁₀H₁₈O₂
• 分子量: 170.252
• InChiKey: YVCUGZBVCHODNB-QXFUBDJGSA-N

物化性质

• 熔点：
  94 °C(Solv: hexane (110-54-3))
• 沸点：
  238.7±8.0 °C(Predicted)
• 密度：
  1.037±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  12
• 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：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (-)-(1R,2R,4S)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane-6-ol 生成 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-6-one
  参考文献：
  名称：

  PAYNE, G. B.;POWELL, J. E.

  摘要：

  DOI：
• 作为产物：
  描述：

  α-松油醇 在 monoperoxyphthalic acid 作用下， 生成 (-)-(1R,2R,4S)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane-6-ol
  参考文献：
  名称：

  Carman, Raymond M.; Fletcher, Mary T., Australian Journal of Chemistry, 1984, vol. 37, # 5, p. 1117 - 1122

  摘要：

  DOI：

文献信息

• Cloning, Expression and Purification of Cindoxin, an Unusual Fmn-Containing Cytochrome P450 Redox Partner
  作者：David B. Hawkes、Kate E. Slessor、Paul V. Bernhardt、James J. De Voss

  DOI：10.1002/cbic.201000119

  日期：——

  Living in cin: Cindoxin is an FMN‐containing cytochrome P450 redox partner that mediates the transfer of electrons derived ultimately from NADPH to P450cin, which then catalyses the enantiospecific hydroxylation of cineole. The P450cin/cindoxin system is unique and represents a new cytochrome P450/redox partner class.

  生活在cin中：Cindoxin是一种含FMN的细胞色素P450氧化还原伙伴，它介导最终将NADPH衍生的电子转移至P450 cin，然后催化桉树脑的对映体特异性羟基化。P450 cin / cindoxin系统是独特的，代表了新的细胞色素P450 /氧化还原伴侣类别。
• Carbonyl transposition and regio- and stereo-specific syntheses of new alcohols, amino-alcohols, and ketones in the monoterpenoid 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane
  作者：Francesco Bondavalli、Pietro Schenone、Angelo Ranise、Silvia Lanteri

  DOI：10.1039/p19800002626

  日期：——

  An efficient transposition of carbonyl group R1–CO–CH2–R2→ R1–CH2–CO–R2 in the 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane system was carried out via hydroboration–oxidation of 6-dialkylamino-1,3,3-trimethyl-2-oxabicyclo[2.2.2]oct-5-enes (3a–c), which gave regio- and stereo-specifically 6-cis-dialkylamino-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-5-trans-ols (4a–c) in high yield. Cope reaction of the

  在1,3,3-三甲基-2-氧杂双环[2.2.2]辛烷体系中进行了羰基基团R 1 –CO–CH 2 –R 2 → R 1 –CH 2 –CO–R 2的有效置换。通过氢硼化-氧化6-二烷基氨基-1,3,3-三甲基-2-恶二环[2.2.2]辛-5-烯（3a–c），得到区域和立体特异性的6-顺式-二烷基氨基- 1,3,3-三甲基-2-氧杂双环[2.2.2] octan -5-反式-ols（4a–c）高产率。应对氮的反应由氨基醇（4b）与过氧化氢制得的一氧化碳（5b）生成1,3,3-三甲基-2-氧杂双环[2.2.2]辛基-5-酮（6），这是其另一种可能的异构体众所周知的1,3,3-三甲基-2-氧杂双环[2.2.2] octan-6-one（1b）。酮（6）还由1,3,3-三甲基-2-氧杂双环[2.2.2]辛-5-烯（2）通过其反式环氧化物（11），氢化铝锂在160-165的还原度制得。其℃得到立体和区域特异性的1
• Roles of cytochrome P450 3A enzymes in the 2-hydroxylation of 1,4-cineole, a monoterpene cyclic ether, by rat and human liver microsomes
  作者：M. Miyazawa、M. Shindo、T. Shimada

  DOI：10.1080/00498250110065595

  日期：2001.1

  involved in the 2-hydroxylation of 1,4-cineole by human liver microsomes, based on the following lines of evidence. First, 1,4-cineole 2-hydroxylation activities catalysed by human liver microsomes were inhibited by ketoconazole, a potent inhibitor of CYP3A activities, and an anti-CYP3A4 antibody. Second, there was a good correlation beteeen CYP3A4 contents and 1,4-cineole 2-hydroxylation activities in

  1.在大鼠和人肝微粒体中研究了1,4-桉树脑（一种单萜环醚）的氧化作用，并在昆虫细胞中表达了重组细胞色素P450（P450或CYP）酶，其中引入了人P450和NADPH-P450还原酶cDNA 。通过气相色谱/质谱分析，确定2-和-exo-hydroxy-1,4-cineole是大鼠和人P450酶催化的1,4-cineole的主要氧化产物。2.根据以下证据，CYP3A4是一种主要的酶，参与人肝微粒体对1，4-桉树脑的2-羟基化反应。首先，人肝微粒体催化的1,4-桉树脑2-羟基化活性被酮康唑（一种有效的CYP3A活性抑制剂）和抗CYP3A4抗体抑制。其次，CYP3A4的含量与1之间存在良好的相关性，检查的十八个人类样本的肝微粒体中的4-cineole 2-羟化活性。最后，在所检查的10种重组人P450酶中，CYP3A4对1,4-桉树脑2-羟基化的活性最高。3.孕烯醇酮16α-腈和地塞米松在大鼠中诱导了肝微粒体1
• Cytochrome P450cin (CYP176A), Isolation, Expression, and Characterization
  作者：David B. Hawkes、Gregory W. Adams、Alma L. Burlingame、Paul R. Ortiz de Montellano、James J. De Voss

  DOI：10.1074/jbc.m203382200

  日期：2002.8

  DNA fragment containing the cytochrome P450(cin) gene (cinA). Sequencing revealed three open reading frames that were identified on the basis of sequence homology as a cytochrome P450, an NADPH-dependent flavodoxin/ferrodoxin reductase, and a flavodoxin. This arrangement suggests that P450(cin) may be the first isolated P450 to use a flavodoxin as its natural redox partner. Sequencing also identified

  细胞色素P450是血蛋白超家族的成员，参与了真核生物和原核生物中各种生理和异种生物化合物的氧化代谢。对细菌P450的研究，特别是涉及单萜氧化的P450的研究，为我们对这些蛋白质的理解提供了不可或缺的贡献，而不再涉及真核生物形式所遇到的问题。我们在这里报告了一种新型的细胞色素P450（P450（cin），CYP176A1），它是从巴西柠檬酸杆菌菌株中纯化的，该菌株能够使用桉树脑1作为其唯一的碳和能量来源。该酶已纯化至均一，并确定了三种胰蛋白酶肽的氨基酸序列。通过使用此信息，开发了基于PCR的克隆策略，该策略允许分离包含细胞色素P450（cin）基因（cinA）的4-kb DNA片段。测序揭示了三个开放阅读框，其根据序列同源性被鉴定为细胞色素P450，NADPH依赖的黄酮毒素/铁氧还蛋白还原酶和黄酮毒素。这种安排表明，P450（cin）可能是第一个使用黄酮毒素作为其天然氧化还原伴侣的分离出的P
• Enantiomeric Purity and Odor Characteristics of 2- and 3-Acetoxy-1,8-cineoles in the Rhizomes of <i>Alpinia </i><i>g</i><i>alanga</i> Willd.
  作者：Kikue Kubota、Yuki Someya、Reiko Yoshida、Akio Kobayashi、Tetsu-ichiro Morita、Hiroyuki Koshino

  DOI：10.1021/jf9807465

  日期：1999.2.1

  (S)-(+)-O-methylmandelate esters of trans- and cis-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-5- and 6-ols (2- and 3-hydroxy-1,8-cineoles) were prepared, and eight diastereomers were separated. The absolute configuration of the asymmetric carbons of the cineole moiety of each diastereomer was determined by H-1 NMR data according to the Mosher theory. Each mandelate was reduced with LiAlHe4 to obtain optically pure hydroxy-1,8-cineoles, this being followed by acetylation to afford optically pure acetoxy-1,8-cineoles. These acetates were subjected to chiral GC, using a cyclodextrin column, and the enantiomeric purity of trans- and cis-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-5- and 6-yl acetates in the aroma concentrate from the rhizomes of Alpinia galanga was determined as 93.9 (5S), 19.4 (5R), 63.5 (6R), and 100 (6R) % cc, respectively. The aroma character of each enantiomer was also evaluated by GC-sniffing.