咖啡酰基乙醇 | 3598-26-3

• 物质功能分类: 有机原料 - 醇、酚、酚醇类化合物及衍生物
• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂醇
• 中文名称: 咖啡酰基乙醇
• 英文名称: caffeoyl alcohol
• 英文别名: caffeic alcohol；caffeoyl alcoho；caffeyl alcohol；1,2-Benzenediol, 4-[(1E)-3-hydroxy-1-propenyl]-；4-(3-hydroxyprop-1-enyl)benzene-1,2-diol
• CAS: 3598-26-3
• 化学式: C₉H₁₀O₃
• 分子量: 166.177
• InChiKey: ZCKDCRKBURQZPT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  60.7
• 氢给体数：
  3
• 氢受体数：
  3

安全信息

• WGK Germany：
  3
• 储存条件：
  室温

制备方法与用途

caffeoyl alcohol 是构成儿茶素木质素（catechyl lignin）的基本单元。catechyl lignin 是由咖啡醇（caffeyl alcohol）通过线性聚合形成的，它是一种天然存在的碳纤维和高价值化学品的重要来源。

反应信息

• 作为反应物：
  描述：

  咖啡酰基乙醇 在 allylphenol synthase from Larreatri dentata 、 Larrea tridentata cinnamyl alcohol acyltransferase-1 、 还原型辅酶Ⅰ 作用下， 以 aq. buffer 为溶剂， 反应 0.5h， 生成 4-propenylcatechol
  参考文献：
  名称：

  Allyl/propenyl phenol synthases from the creosote bush and engineering production of specialty/commodity chemicals, eugenol/isoeugenol, in Escherichia coli

  摘要：

  The creosote bush (Larrea tridentata) harbors members of the monolignol acyltransferase, allylphenol synthase, and propenylphenol synthase gene families, whose products together are able to catalyze distinct regiospecific conversions of various monolignols into their corresponding allyl- and propenyl-phenols, respectively. In this study, co-expression of a monolignol acyltransferase with either substrate versatile allylphenol or propenylphenol synthases in Escherichia coli established that various monolignol substrates were efficiently converted into their corresponding allyl/propenyl phenols, as well as providing proof of concept for efficacious conversion in a bacterial platform. This capability thus potentially provides an alternate source to these important plant phytochemicals, whether for flavor/fragrance and fine chemicals, or ultimately as commodities, e.g., for renewable energy or other intermediate chemical purposes. Previous reports had indicated that specific and highly conserved amino acid residues 84 (Phe or Val) and 87 (Ile or Tyr) of two highly homologous allyl/propenyl phenol synthases (circa 96% identity) from a Clarkia species mainly dictate their distinct regiospecific catalyzed conversions to afford either allyior propenyl-phenols, respectively. However, several other allyl/propenyl phenol synthase homologs isolated by us have established that the two corresponding amino acid 84 and 87 residues are not, in fact, conserved. (C) 2013 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.abb.2013.10.019
• 作为产物：
  描述：

  TRANS-咖啡酸 在 Escherichia coli BL₂₁-Gold(DE₃) lacI^Q₁ pALXtreme-tal-4cl-ccr-cad 作用下， 反应 17.0h， 生成 咖啡酰基乙醇
  参考文献：
  名称：

  大肠杆菌天然和非天然单酚的微生物生产。

  摘要：

  苯丙类和苯丙类衍生的植物多酚在食品和制药工业中有许多应用。近年来，已经对几种微生物平台生物进行了工程改造以生产此类化合物。然而，在大多数情况下，微生物（多）苯酚的生产是受自然界启发的，因此迄今为止，主要生产的是天然存在的化合物。在这里，我们利用了参与苯丙氨酸合成的酶的混杂性，并利用了带有合成单木酚途径的工程化大肠杆菌菌株的多功能性，将添加的天然和非天然苯丙酸转化为其相应的单木酚。

  DOI：

  10.1002/cbic.201800673

文献信息

• Insights into lignin primary structure and deconstruction from Arabidopsis thaliana COMT (caffeic acid O-methyl transferase) mutant Atomt1
  作者：Syed G. A. Moinuddin、Michaël Jourdes、Dhrubojyoti D. Laskar、Chanyoung Ki、Claudia L. Cardenas、Kye-Won Kim、Dianzhong Zhang、Laurence B. Davin、Norman G. Lewis

  DOI：10.1039/c004817h

  日期：——

  The Arabidopsis mutant Atomt1 lignin differs from native lignin in wild type plants, in terms of sinapyl (S) alcohol-derived substructures in fiber cell walls being substituted by 5-hydroxyconiferyl alcohol (5OHG)-derived moieties. During programmed lignin assembly, these engender formation of benzodioxane substructures due to intramolecular cyclization of their quinone methides that are transiently formed following 8-O-4′ radical-radical coupling. Thioacidolytic cleavage of the 8-O-4′ inter-unit linkages in the Atomt1 mutant, relative to the wild type, indicated that cleavable sinapyl (S) and coniferyl (G) alcohol-derived monomeric moieties were stoichiometrically reduced by a circa 2 : 1 ratio. Additionally, lignin degradative analysis resulted in release of a 5OHG–5OHG–G trimer from the Atomt1 mutant, which then underwent further cleavage. Significantly, the trimeric moiety released provides new insight into lignin primary structure: during polymer assembly, the first 5OHG moiety is linked via a C8–O–X inter-unit linkage, whereas subsequent addition of monomers apparently involves sequential addition of 5OHG and G moieties to the growing chain in a 2 : 1 overall stoichiometry. This quantification data thus provides further insight into how inter-unit linkage frequencies in native lignins are apparently conserved (or near conserved) during assembly in both instances, as well as providing additional impetus to resolve how the overall question of lignin macromolecular assembly is controlled in terms of both type of monomer addition and primary sequence.

  拟南芥突变体 Atomt1 木质素与野生型植物中的原生木质素不同，纤维细胞壁中由 sinapyl (S) 醇衍生的亚结构被 5-hydroxyconiferyl 醇 (5OHG) 衍生的分子取代。在木质素的程序化组装过程中，由于 8-O-4′ 自由基-自由基偶联后瞬时形成的醌基甲烷的分子内环化作用，这些醌基甲烷会形成苯并二恶烷亚结构。与野生型相比，Atomt1 突变体中 8-O-4′ 单元间连接的硫代酸裂解表明，可裂解的桧醇（S）和松柏醇（G）衍生的单体分子以约 2 ：1 的比例减少。此外，木质素降解分析还导致 Atomt1 突变体释放出 5OHG-5OHG-G 三聚体，然后进一步裂解。值得注意的是，释放出的三聚体提供了对木质素一级结构的新认识：在聚合物组装过程中，第一个 5OHG 分子通过 C8-O-X 单元间连接，而随后单体的添加显然涉及 5OHG 和 G 分子以 2 ：1 的总比例。因此，这些定量数据让我们进一步了解了在这两种情况下，原生木质素中的单元间连接频率是如何在组装过程中保持不变（或接近不变）的，同时也为解决木质素大分子组装的整体问题提供了更多动力，即单体添加类型和主序是如何受控的。
• Kinetics and Mechanism for the Scavenging Reaction of the 2,2-Diphenyl-1-picrylhydrazyl Radical by Synthetic Artepillin C Analogues
  作者：Tomonori Kawashima、Sushma Manda、Yoshihiro Uto、Kei Ohkubo、Hitoshi Hori、Ken-ichiro Matsumoto、Kiyoshi Fukuhara、Nobuo Ikota、Shunichi Fukuzumi、Toshihiko Ozawa、Kazunori Anzai、Ikuo Nakanishi

  DOI：10.1246/bcsj.20120005

  日期：2012.8.15

  The kinetics for the reaction of the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH•) with artepillin C, a prenylated phenylpropanoid found specifically in Brazilian propolis, and its analogues was examined in deaerated acetonitrile (MeCN) to shed light on the mechanism for the radical-scavenging reaction of phenolic antioxidants as well as on the structure–activity relationship. Among the examined analogues, a compound having a catechol moiety is found to have the largest second-order rate constant (k) for the DPPH•-scavenging reaction. The deuterium kinetic isotope effect of 1.6 was observed for the DPPH•-scavenging reaction of artepillin C in the presence of 0.13 M CD3OD or CH3OH in deaerated MeCN at 298 K. The log k values were found to be linearly correlated with calculated energy difference values (DHT, HT: hydrogen transfer) between the artepillin C analogues and the corresponding phenoxyl radicals, while such a linear correlation cannot be observed between the log k values and calculated ionization potentials (IP), DHT − IP, or experimental one-electron-oxidation potentials of the artepillin C analogues. These results together with a calculated structure of the transition state for the reaction between the artepillin C analogue and DPPH• suggest that the DPPH•-scavenging reaction of the artepillin C analogues in deaerated MeCN proceeds via a one-step hydrogen-atom transfer from the phenolic OH group to DPPH• rather than an electron transfer followed by proton transfer.

  在脱气乙腈 (MeCN) 中检查了 2,2-二苯基-1-三硝基苯肼基 (DPPH•) 与阿替匹林 C 的反应动力学，阿替匹林 C 是巴西蜂胶中特有的一种异戊二烯化苯丙素及其类似物。酚类抗氧化剂自由基清除反应的机理以及构效关系。在所检查的类似物中，发现具有儿茶酚部分的化合物对于DPPH·清除反应具有最大的二级速率常数(k)。在 0.13 M CD3OD 或 CH3OH 存在的脱气 MeCN 中，298 K 下，观察到阿替匹林 C 的 DPPH·清除反应为 1.6 的氘动力学同位素效应。发现 log k 值与计算的能量差值线性相关（DHT，HT：氢转移）在artepillin C类似物和相应的苯氧基自由基之间，而log k值和计算的电离势（IP）、DHT - IP或实验单电子之间无法观察到这种线性相关性artepillin C 类似物的氧化电位。这些结果以及计算出的阿替林 C 类似物与 DPPH• 之间反应的过渡态结构表明，阿替林 C 类似物在脱气 MeCN 中的 DPPH• 清除反应是通过一步氢原子转移进行的。酚OH基团转移至DPPH•，而不是先进行电子转移，然后进行质子转移。
• Organoborane-catalysed reductive depolymerisation of catechyl lignin under ambient conditions
  作者：Shihao Su、Fan-shu Cao、Shuizhong Wang、Qingru Shen、Gen Luo、Qiang Lu、Guoyong Song

  DOI：10.1039/d3gc02025h

  日期：——

  C-lignin biopolymers can be efficiently depolymerized into catechol derivatives with 85% yield and 91% selectivity at room temperature and ambient pressure in highly concentrated form (300 mg mL⁻¹) over an organoborane catalyst.

  在室温和常压条件下，C-木质素生物聚合物在有机硼烷催化剂的作用下，以高浓度形式（300 毫克/毫升-1）高效解聚成邻苯二酚衍生物，产率为 85%，选择性为 91%。
• Anaerobic demethylation of guaiacyl-derived monolignols enabled by a designed artificial cobalamin methyltransferase fusion enzyme
  作者：Christopher Grimm、Simona Pompei、Kristina Egger、Michael Fuchs、Wolfgang Kroutil

  DOI：10.1039/d2ra08005b

  日期：——

  Lignin-derived aryl methyl ethers (e.g. coniferyl alcohol, ferulic acid) are expected to be a future carbon source for chemistry. The well-known P450 dependent biocatalytic O-demethylation of these aryl methyl ethers is prone to side product formation especially for the oxidation sensitive catechol products which get easily oxidized in the presence of O2. Alternatively, biocatalytic demethylation using

  木质素衍生的芳基甲基醚（例如针叶醇、阿魏酸）有望成为未来的化学碳源。众所周知的这些芳基甲基醚的 P450 依赖性生物催化 O 去甲基化容易形成副产物，特别是对于在 O2 存在下容易氧化的氧化敏感的邻苯二酚产物。或者，可以在厌氧条件下使用钴胺依赖性酶进行生物催化去甲基化，其中需要两种蛋白质，即甲基转移酶和载体蛋白。为了使这种方法适用于制备转化，设计了融合蛋白，通过可变甘氨酸接头将钴胺依赖性甲基转移酶 （MT） 与来自哈夫尼斯脱硫杆菌的类蛋白结合蛋白 （CP） 连接起来。从产生的蛋白质来看，具有最短接头的融合酶 MT-L5-CP 在研究的所有融合酶中表现最好，显示出与分离的蛋白质相当甚至更好的性能。融合酶具有多种优势，例如可以跳过 CP 最初所需的钴胺素辅因子上样步骤，从而大大简化了方案。因此，使用 Schlenk 条件进行生物催化去甲基化，允许 O 去甲基化，例如在 25 mL 比例上对单木质素针叶醇进行
• A Continuous, Quantitative Fluorescent Assay for Plant Caffeic Acid <i>O</i>-Methyltransferases
  作者：Nathan A. Palmer、Scott E. Sattler、Aaron J. Saathoff、Gautam Sarath

  DOI：10.1021/jf904445q

  日期：2010.5.12

  Plant caffeic acid O-methyltransferases (COMTs) use S-adenosylmethionine (ado-met), as a methyl donor to transmethylate their preferred (phenolic) substrates in vivo, and will generally utilize a range of phenolic compounds in vitro. Collazo et al. (Anal. Biochem. 2005, 342, 86-92) have published a discrete, end-point fluorescence assay to detect histone methyltransferases using S-adenosyl homocysteine hydrolase and adeonsine deaminase as coupling enzymes and a thiolspecific fluorophore, Thioglo1, as the detecting reagent. Using this previous assay as a guide, we have developed and validated a facile, sensitive and real-time fluorescence assay for characterizing plant COMTs and in the process simplified the original assay as well by obviating the need for adenosine deaminase in the assay, and simultaneously converting an end-point assay into a continuous one. Our assay has been used to kinetically characterize recombinant sorghum COMT (Bmr-12) a key enzyme involved in cell wall lignification, and analyze COMT activity in maturing tillers from switchgrass plants. Data indicated that the calculated K-m and V-max values for the recombinant sorghum COMT using different substrates in the fluorescent assay were similar to published values for COMT enzymes from other plant species. Native COMT activity was greatest in internodes at the top of a tiller and declined in the more basal internodes. This new assay should have broad applicability for characterizing COMTs and potentially other plant methlytransferases that utilize ado-met as a methyl donor.