sinapyl acetate

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: sinapyl acetate
• 英文别名: 3-(4-Hydroxy-3,5-dimethoxyphenyl)prop-2-enyl acetate
• 化学式: C₁₃H₁₆O₅
• 分子量: 252.267
• InChiKey: JMBAYAOTPDVMAE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  sinapyl acetate 在 allylphenol synthase from Larreatri dentata 、 还原型辅酶Ⅰ 作用下， 以 aq. buffer 为溶剂， 生成 4-丙烯基-2,6-二甲氧基苯酚
  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：

  3-[4-(乙酰氧基)-3,5-二甲氧基肉桂酸 在 吡啶 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 乙酸肼 、 三乙胺 作用下， 以 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， 反应 25.5h， 生成 sinapyl acetate
  参考文献：
  名称：

  Preparation of monolignol γ-acetate, γ-p-hydroxycinnamate, and γ-p-hydroxybenzoate conjugates: selective deacylation of phenolic acetates with hydrazine acetate

  摘要：

  我们在这里报告了一种可靠且简便的合成方法，可以合成一系列单酚γ-p-羟基肉桂酸盐（包括p-香豆酸、香豆酸盐和咖啡酸盐）、γ-醋酸盐和γ-p-羟基苯甲酸盐结合物，许多尚未被报道过。这些化合物可能是天然木质素生物合成过程中的中间体，或是即将用于设计木质素的新单体结合物。关键在于开发了一种高选择性的酚酸酯去酰基化方法；即一种能够切割酚酸酯，同时保持敏感的单酚酯结合物不被破坏的方法。

  DOI：

  10.1039/c3ra42818d

文献信息

• Novel tetrahydrofuran structures derived from β–β-coupling reactions involving sinapyl acetate in Kenaf lignins
  作者：Fachuang Lu、John Ralph

  DOI：10.1039/b809464k

  日期：——

  Free radical coupling of sinapyl γ-acetate or cross-coupling between sinapyl acetate and sinapyl alcohol yields novel tetrahydrofuran β–β-(cross-)coupled dehydrodimers. Such substructures are therefore anticipated in naturally acetylated lignins, e.g. in Kenaf, if sinapyl acetate is a component of the lignin monomer pool. The DFRC (derivatization followed by reductive cleavage) method, modified by replacing all acetyl reagents and solvents with their propionyl analogs (DFRC′), allows the analysis of naturally acetylated lignins. DFRC′ treatment of the sinapyl acetate-derived dimers or crossed dimers gave diagnostic products that retain at least one acetate group on a sidechain γ-position; the products have been authenticated by comparison of their mass spectra and GC retention times with those of synthesized compounds. DFRC′ of Kenaf lignins produces the same diagnostic products as from the dimers, implicating the presence of the various tetrahydrofuran units in Kenaf lignins. With data from the model compounds in hand, NMR analysis of Kenaf lignins elegantly confirms the presence of such substructures in the polymer, establishing that acetates on Kenaf lignins arise through incorporation of sinapyl acetate, as a lignin precursor, via enzyme-mediated radical coupling mechanisms.

  自由基耦合愈創木基γ-醋酸酯或愈創木醋酸酯与愈創木醇之间的交叉耦合，可以生成新型的四氢呋喃β-β-(交叉)耦合去氢二聚体。因此，预期在天然醋酸化木质素中会出现这样的亚结构，例如在麻中，如果愈创木醋酸酯是木质素单体池的组成部分。DFRC（衍生化后还原裂解）方法通过用其丙酸酯类似物替代所有醋酸试剂和溶剂（DFRC'）进行改进，使得能够分析天然醋酸化木质素。对由愈创木醋酸酯衍生的二聚体或交叉二聚体进行DFRC'处理得到了诊断产品，这些产品在侧链γ位置至少保留一个醋酸基；通过与合成化合物的质谱和气相色谱保留时间的比较，确认了这些产品。对麻木质素进行DFRC'处理，产生与二聚体相同的诊断产品，表明麻木质素中存在各种四氢呋喃单元。根据模型化合物的数据，NMR分析麻木质素优雅地确认了这些亚结构在聚合物中的存在，证实麻木质素上的醋酸盐是通过作为木质素前体的愈创木醋酸酯，通过酶介导的自由基耦合机制的方式引入的。
• Biomimetic Oxidation of Monolignol Acetate and <i>p</i>-Coumarate by Silver Oxide in 1,4-Dioxane
  作者：Ayana Yamashita、Takao Kishimoto、Masahiro Hamada、Noriyuki Nakajima、Daisuke Urabe

  DOI：10.1021/acs.jafc.9b07682

  日期：2020.2.19

  Lignin acylated with acetate and/or p-coumarate is common in many herbaceous plants. Herein, the biomimetic oxidation of γ-acylated monolignols with Ag2O was studied to understand the effect of γ-acyl groups on monolignol polymerization. The oxidation of sinapyl acetate gave γ-acylated and α-acylated β-O-4 dimers in 71 and 9.5% yields, respectively. The oxidation of sinapyl p-coumarate produced γ-acylated

  用乙酸盐和/或对香豆酸盐酰化的木质素在许多草本植物中很常见。在本文中，研究了用Ag2O仿生氧化γ-酰化的单木质醇，以了解γ-酰基对单木质醇聚合的影响。乙酸芥子酸酯的氧化分别以71和9.5％的产率得到γ-酰化的和α-酰化的β-O-4二聚体。芥子酸对香豆酸酯的氧化分别以53％和16％的产率产生了γ-酰化的β-O-4和γ-酰化的四氢化萘β-β二聚体。仅对-香豆酸酯中的芥子醇部分反应，并且对-香豆酸酯部分保持不变，这表明对香豆酸未结合到酰化的木质素中的木质素主链中。本研究中使用的所有γ-酰化单木酚均生成γ-酰化的β-O-4二聚体，这表明γ-酰化的单木酚充当木质素单体。
• DFRC Method for Lignin Analysis. 1. New Method for β-Aryl Ether Cleavage:  Lignin Model Studies
  作者：Fachuang Lu、John Ralph

  DOI：10.1021/jf970539p

  日期：1997.12.1

  A new method for selective and efficient cleavage of arylglycerol-beta-aryl (beta-O-4) ether linkages in lignins is described and applied to several Lignin beta-ether models. The term "DFRC" was coined for derivatization followed by reductive cleavage. Derivatization, accompanied by cell wall solubilization, is accomplished with acetyl bromide (AcBr); reductive cleavage of resulting beta-bromo ethers utilizes zinc in acetic acid. Degradation monomers, 4-acetoxycinnamyl acetates, from beta-ether cleavage by the DFRC method were identified by NMR, CC-MS, and comparison of GC retention times with authentic compounds. Under the conditions used in this study, the beta-ether linkage of all models was cleaved in very high (> 92%) yield. The DFRC method produces simpler mixtures of monomers with higher yields than alternative hydrolytic methods. Because of its relative simplicity, mild conditions, and exceptional selectivity, this method should become a powerful analytical method for lignin characterization.
• Preparation of monolignol γ-acetate, γ-p-hydroxycinnamate, and γ-p-hydroxybenzoate conjugates: selective deacylation of phenolic acetates with hydrazine acetate
  作者：Yimin Zhu、Matthew Regner、Fachuang Lu、Hoon Kim、Allison Mohammadi、Timothy J. Pearson、John Ralph

  DOI：10.1039/c3ra42818d

  日期：——

  We report here a reliable and facile synthesis of a range of monolignol γ-p-hydroxycinnamate (including p-coumarate, ferulate, and caffeate), γ-acetate, and γ-p-hydroxybenzoate conjugates, many not previously reported, that are either putative intermediates in the biosynthesis of natural lignins or new monomer-conjugates destined for upcoming designer lignins. The key was the development of a highly selective deacylation approach for phenolic acetates; i.e., a method that cleaves phenolic acetates while leaving the sensitive monolignol ester conjugates intact.

  我们在这里报告了一种可靠且简便的合成方法，可以合成一系列单酚γ-p-羟基肉桂酸盐（包括p-香豆酸、香豆酸盐和咖啡酸盐）、γ-醋酸盐和γ-p-羟基苯甲酸盐结合物，许多尚未被报道过。这些化合物可能是天然木质素生物合成过程中的中间体，或是即将用于设计木质素的新单体结合物。关键在于开发了一种高选择性的酚酸酯去酰基化方法；即一种能够切割酚酸酯，同时保持敏感的单酚酯结合物不被破坏的方法。
• Allyl/propenyl phenol synthases from the creosote bush and engineering production of specialty/commodity chemicals, eugenol/isoeugenol, in Escherichia coli
  作者：Sung-Jin Kim、Daniel G. Vassão、Syed G.A. Moinuddin、Diana L. Bedgar、Laurence B. Davin、Norman G. Lewis

  DOI：10.1016/j.abb.2013.10.019

  日期：2014.1

  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.