14,15-epoxygeranylgeraniol | 41370-60-9

• 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: 14,15-epoxygeranylgeraniol
• 英文别名: 13-(3,3-Dimethyloxiranyl)-3,7,11-trimethyl-2,6,10-tridecatrien-1-ol；(2E,6E,10E)-13-(3,3-dimethyloxiran-2-yl)-3,7,11-trimethyltrideca-2,6,10-trien-1-ol
• CAS: 41370-60-9
• 化学式: C₂₀H₃₄O₂
• 分子量: 306.489
• InChiKey: XCSZPKBSRHYGDR-OGJIFNPOSA-N

物化性质

• 沸点：
  408.0±35.0 °C(Predicted)
• 密度：
  0.931±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  22
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  32.8
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  14,15-epoxygeranylgeraniol 在 sodium tetrahydroborate 、 4-甲基苯磺酸吡啶 、 过碘酸 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 水 、 二甲基亚砜 为溶剂， 反应 47.0h， 生成 (E,E,E)-5,9,13-trimethyl-15-[(tetrahydro-2H-pyran-2-yl)oxy]pentadeca-5,9,13-trienenitrile
  参考文献：
  名称：

  Novel Regio- and Stereoselective Cascade 6-endo-trig Cyclisations from Polyene Acyl Radical Intermediates Leading to Steroid-Like Pentacycles and Heptacycles

  摘要：

  In a quite remarkable regio- and stereoselective manner, each of the (all-E)-polyene selenoates 5a-c is shown to undergo cascade radical-mediated polycyclisations via consecutive 6-endo-trig reactions, leading to the corresponding all-trans, anti, tri-, penta- and heptacycles, i.e., 20, 23, and 25, in good yields. The configurations of these 'steroid-like' polycycles followed from detailed examination and correlation of chemical shift data in their C-13-NMR spectra.

  DOI：

  10.1002/1522-2675(20000906)83:9<2629::aid-hlca2629>3.0.co;2-w
• 作为产物：
  描述：

  香叶基香叶醇 在 吡啶 、 N-溴代丁二酰亚胺(NBS) 、 potassium carbonate 作用下， 反应 5.0h， 生成 14,15-epoxygeranylgeraniol
  参考文献：
  名称：

  Synthesis of lurlene, the sex pheromone of the green flagellate Chlamydomonas allensworthii

  摘要：

  Lurlene [(4E,8E,12E)-14-[2'-hydroxy-3',4'-dimethyl-5'-(1 ''-beta-D-xylopyranosyloxy)phenyl]-4,8,12-trimethyltetradeca-4,8,12-trienoic acid, 1], the sex pheromone produced by the female gametes of Chlamydomonas allensworthii, was synthesized as a mixture of 1 and its (12Z)-isomer, and the mixture was bioactive.

  DOI：

  10.1016/0040-4039(96)00127-x

文献信息

• A Strategy for Position-Selective Epoxidation of Polyprenols
  作者：Vijay Gnanadesikan、E. J. Corey

  DOI：10.1021/ja801899v

  日期：2008.6.1

  developed for the efficient site-selective epoxidation of poylolefinic isoprenoid alcohols, based on the use of an internal control element for intramolecular reaction. The approach is illustrated by application to a series of polyisoprenoid alcohols (polyprenols) at substrate concentration of 0.5 mM. With polyprenol substrates having the hydroxyl function at one terminus, the internal epoxidation can be directed

  基于使用内部控制元件进行分子内反应，已开发出一种有效的策略，用于聚烯烃类异戊二烯醇的有效位点选择性环氧化。该方法通过应用于一系列底物浓度为 0.5 mM 的聚异戊二烯醇（聚异戊二烯醇）来说明。对于在一个末端具有羟基官能团的聚异戊二烯醇底物，内部环氧化作用可针对聚异戊二烯醇的双键，该双键距末端羟基异戊二烯亚单元四或五处。
• Biomimetic Cyclization of Epoxide Precursors of Indole Mono-, Sesqui- and Diterpene Alkaloids by Lewis Acids
  作者：Tetsuya ISAKA、Morifumi HASEGAWA、Hiroaki TOSHIMA

  DOI：10.1271/bbb.110511

  日期：2011.11.23

  Cyclization of the synthesized epoxide precursors of indole mono-, sesqui- and diterpene alkaloids was performed to elucidate the mechanism for biomimetic cationic cyclization to polycyclic structures. 3-(6,7-Epoxygeranyl)indole (11), 3-(10,11-epoxyfarnesyl)indole (2) and 3-(14,15-epoxygeranylgeranyl)indole (3) were respectively synthesized from geraniol, farnesol and geranylgeraniol in 6 or 7 steps

  进行吲哚单，倍半萜和二萜生物碱的合成环氧化物前体的环化，以阐明将仿生阳离子环化为多环结构的机理。分别由香叶醇，法呢醇和香叶基香叶醇合成3-（6,7-环氧香叶基）吲哚（11），3-（10,11-环氧法尼基）吲哚（2）和3-（14,15-环氧香叶基香叶基）吲哚（3）。分6步或7步。四个路易斯酸（MeAlCl（2），BF（3）·OEt（2），TiCl（4）和SnCl（4））用于合成环氧化物前体的仿生环化。色谱分离后，分离出环化产物（一种产物来自11种，两种产物来自2种，三种产物来自3种）。使用NMR（COSY，HSQC，HMBC，NOESY等）和HRMS分析确定其结构。结果表明仿生环化产生了类似于天然吲哚萜烯生物碱的新的多环化合物。我们得出结论，当使用路易斯酸时，阳离子中间体的稳定性应确定通过仿生环化形成产物的偏好。
• Combinatorial evolution of site- and enantioselective catalysts for polyene epoxidation
  作者：Phillip A. Lichtor、Scott J. Miller

  DOI：10.1038/nchem.1469

  日期：2012.12

  Selectivity in the catalytic functionalization of complex molecules is a major challenge in chemical synthesis. The problem is magnified when there are several possible stereochemical outcomes and when similar functional groups occur repeatedly within the same molecule. Selective polyene oxidation provides an archetypical example of this challenge. Historically, enzymatic catalysis has provided the only precedents. Although non-enzymatic catalysts that meet some of these challenges became known, a comprehensive solution has remained elusive. Here, we describe low molecular weight peptide-based catalysts, discovered through a combinatorial synthesis and screening protocol, that exhibit site- and enantioselective oxidation of certain positions of various isoprenols. This diversity-based approach, which exhibits features reminiscent of the directed evolution of enzymes, delivers catalysts that compare favourably to the state-of-the-art for the asymmetric oxidation of these compounds. Moreover, the approach culminated in catalysts that exhibit alternative-site selectivity in comparison to oxidation catalysts previously described. Aspartic acid-based catalysts that are selective for oxidation of either the 2,3 position or the 6,7 position of certain isoprenols have been discovered. The catalysts emerged from a diversity-based approach employing the one-bead-one-compound libraries. The site-selectivity of the catalysis seems to derive from the hydroxyl group in the substrate, although the details of this are not yet known.

  复杂分子的催化功能化选择性是化学合成中的一大挑战。当存在多种可能的立体化学结果且同一分子中重复出现类似官能团时，这个问题变得更加严重。选择性多烯氧化为这一挑战提供了一个典型的例子。历史上，酶催化提供了唯一的先例。尽管一些满足这些挑战的非酶催化剂已经被认识到，但全面的解决方案仍然难以实现。在此，我们描述了一种基于低分子量肽的催化剂，这些催化剂是通过组合合成和筛选协议发现的，能够对各种异戊醇的某些位置进行位点和对映体选择性氧化。这种基于多样性的策略，具有与酶的定向进化类似的特征，提供了与这些化合物的不对称氧化的最新技术相当的催化剂。此外，该方法最终得出的催化剂在与之前描述的氧化催化剂相比时展现了替代位点的选择性。我们发现了选择性氧化某些异戊醇的2,3位或6,7位的基于天冬氨酸的催化剂。这些催化剂来源于采用一珠一配体库的多样性基础方法。催化的位点选择性似乎源自底物中的羟基，但其具体细节尚不清楚。
• [EN] BIOSYNTHESIS OF CHEMICALLY DIVERSIFIED NON-NATURAL TERPENE PRODUCTS<br/>[FR] BIOSYNTHÈSE DE PRODUITS TERPÉNIQUES NON NATURELS DIVERSIFIÉS CHIMIQUEMENT
  申请人：UNIV MICHIGAN STATE

  公开号：WO2021092200A1

  公开（公告）日：2021-05-14

  The disclosure relates to compounds of the formulae (l)-(IV) and their use as substrates for making terpenoids. New substrates for terpene biosynthesis and methods for making new types of terpenes are described herein. Diterpenes occupy a unique molecular space with critical pharmaceutical applications over a diverse spectrum including anti-microbial, anti-cancer, immunomodulatory and psychoactive properties.

  该披露涉及公式(l)-(IV)的化合物及其用作合成萜类化合物的底物。本文描述了用于合成萜类化合物的新底物以及制备新类型萜类化合物的方法。二萜类化合物占据了一个独特的分子空间，在包括抗微生物、抗癌、免疫调节和精神活性等广泛领域具有关键的药用应用。
• A simple synthetic process for the elaboration of oligoprenols by stereospecific coupling of di-, tri-, or oligoisoprenoid units
  作者：E.J. Corey、Wen-Chung Shieh

  DOI：10.1016/s0040-4039(00)79008-3

  日期：1992.10

  An effective method of allyl-allyl coupling which is position and stereospecific leads in a simple way to oligoprenols from E-allylic halides.