(1RS,2SR)-1,2-dihydro-7-hydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-6,8-dimethoxynaphthalene-2,3-dicarboxylic acid dimethyl ester

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 芳基四氢萘木脂素
• 英文名称: (1RS,2SR)-1,2-dihydro-7-hydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-6,8-dimethoxynaphthalene-2,3-dicarboxylic acid dimethyl ester
• 英文别名: trans-thomasidioic acid dimethyl ester；dimethyl (±)-thomasidioate；thomasidioic acid dimethyl ester；dimethyl (1S,2R)-7-hydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-6,8-dimethoxy-1,2-dihydronaphthalene-2,3-dicarboxylate
• 化学式: C₂₄H₂₆O₁₀
• 分子量: 474.464
• InChiKey: KBCZTZCGEJFBKI-HKUYNNGSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  34
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  130
• 氢给体数：
  2
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  (1RS,2SR)-1,2-dihydro-7-hydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-6,8-dimethoxynaphthalene-2,3-dicarboxylic acid dimethyl ester 在 sodium hydroxide 作用下， 反应 16.0h， 以60%的产率得到trans-7-hydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-6,8-dimethoxy-1,2-dihydronaphthalene-2,3-dicarboxylic acid
  参考文献：
  名称：

  Sinapate Dehydrodimers and Sinapate−Ferulate Heterodimers in Cereal Dietary Fiber

  摘要：

  Two 8-8-coupled sinapic acid dehydrodimers and at least three sinapate-ferulate heterodimers have been identified as saponification products from different insoluble and soluble cereal grain dietary fibers. The two 8-8-disinapates were authenticated by comparison of their GC retention times and mass spectra with authentic dehydrodimers synthesized from methyl or ethyl sinapate using two different single-electron metal oxidant systems. The highest amounts (481 mug/g) were found in wild rice insoluble dietary fiber. Model reactions showed that it is unlikely that the dehydrodisinapates detected are artifacts formed from free sinapic acid during the saponification procedure. The dehydrodisinapates presumably derive from radical coupling of sinapate-polymer esters in the cell wall; the radical coupling origin is further confirmed by finding 8-8 and 8-5 (and possibly 8-O-4) sinapate-ferulate cross-products. Sinapates therefore appear to have an analogous role to ferulates in cross-linking polysaccharides in cereal grains and presumably grass cell walls in general.

  DOI：

  10.1021/jf020910v
• 作为产物：
  描述：

  3,5-二甲氧基-4-羟基肉桂酸 在 三氯化铁 、 乙酰氯 作用下， 以 甲醇 为溶剂， 反应 64.0h， 生成 (1RS,2SR)-1,2-dihydro-7-hydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-6,8-dimethoxynaphthalene-2,3-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  Sinapate Dehydrodimers and Sinapate−Ferulate Heterodimers in Cereal Dietary Fiber

  摘要：

  Two 8-8-coupled sinapic acid dehydrodimers and at least three sinapate-ferulate heterodimers have been identified as saponification products from different insoluble and soluble cereal grain dietary fibers. The two 8-8-disinapates were authenticated by comparison of their GC retention times and mass spectra with authentic dehydrodimers synthesized from methyl or ethyl sinapate using two different single-electron metal oxidant systems. The highest amounts (481 mug/g) were found in wild rice insoluble dietary fiber. Model reactions showed that it is unlikely that the dehydrodisinapates detected are artifacts formed from free sinapic acid during the saponification procedure. The dehydrodisinapates presumably derive from radical coupling of sinapate-polymer esters in the cell wall; the radical coupling origin is further confirmed by finding 8-8 and 8-5 (and possibly 8-O-4) sinapate-ferulate cross-products. Sinapates therefore appear to have an analogous role to ferulates in cross-linking polysaccharides in cereal grains and presumably grass cell walls in general.

  DOI：

  10.1021/jf020910v

文献信息

• Asymmetric Biomimetic Oxidations of Phenols: The Mechanism of the Diastereo- and Enantioselective Synthesis of Thomasidioic Acid
  作者：Luca Zoia、Maurizio Bruschi、Marco Orlandi、Eeva-Liisa Tolppa、Bruno Rindone

  DOI：10.3390/molecules13010129

  日期：——

  Enantiopure chiral amidic derivatives of sinapic acid were oxidised withhydrogen peroxide using horseradish peroxidase (HRP) as the catalyst to give thearyltetraline dilignol thomasidioic acid. Trans-diastereoselectivity and enantioselectivity inthe formation of thomasidioic acid was observed. Computational methods show that theenantioselectivity is controlled by the β-β oxidative coupling step, while thediastereoselectivity is controlled by the stability of the reactive conformation of theintermediate quinomethide.

  纯对映体的手性酰胺类芥子酸衍生物在辣根过氧化物酶（HRP）催化下，通过过氧化氢氧化生成芳基四氢化茚二联木脂酸托马斯二酸。在托马斯二酸的形成过程中观察到了反式非对映选择性和对映选择性。计算方法表明，对映选择性由β-β氧化偶联步骤控制，而非对映选择性则由中间体醌甲烷的反应构象的稳定性控制。
• 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。
• Synthesis of thomasic acid
  作者：R. Ahmed、M. Lehrer、R. Stevenson

  DOI：10.1016/0040-4020(73)80192-9

  日期：1973.1

  Thomasidioic acid (2) has been synthesized in two steps by oxidative phenol coupling of sinapic acid (6) to the dilactone (7) followed by acid-catalyzed rearrangement. The diol dibenzyl ether (15), derived from thomasidioic acid dimethyl ester (9) by benzylation followed by LAH reduction, was selectively oxidized to yield thomasic acid (1) after debenzylation and base hydrolysis.

  通过将芥子酸（6）氧化苯酚偶联至双内酯（7），然后进行酸催化的重排，通过两个步骤合成了托马斯二酸（2）。脱苄基化和碱水解后，通过苄基化然后通过LAH还原从硫代二酸二甲酯（9）衍生而来的二醇二苄基醚（15）被选择性氧化，生成胸苷酸（1）。
• Setaelae, Harri; Pajunen, Aarne; Kilpelaeinen, Ilkka, Journal of the Chemical Society. Perkin transactions I, 1994, # 9, p. 1163 - 1166
  作者：Setaelae, Harri、Pajunen, Aarne、Kilpelaeinen, Ilkka、Brunow, Goesta

  DOI：——

  日期：——
• Setaelae, Harri; Pajunen, Aarne; Kilpelaeinen, Ilkka, Journal of the Chemical Society. Perkin transactions I, <hi>1994</hi>, # 9, p. 1163 - 1166
  作者：Setaelae, Harri、Pajunen, Aarne、Kilpelaeinen, Ilkka、Brunow, Goesta

  DOI：——

  日期：——