(2R)-3-[(2R,3S)-(5,7,3',4'-tetrakis(methyloxy)-3-hydroxyflavan-8-yl)]-5,7,3',4'-tetramethoxyflavan-3-ene | 1265882-02-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 黄酮类化合物
• 英文名称: (2R)-3-[(2R,3S)-(5,7,3',4'-tetrakis(methyloxy)-3-hydroxyflavan-8-yl)]-5,7,3',4'-tetramethoxyflavan-3-ene
• 英文别名: (2R)-3-[(2R,3S)-5,7,3',4'-tetrakis(methyloxy)-3-hydroxyflavan]-5,7,3',4'-tetrarnethoxyflavan-3-ene；(2R,3S)-2-(3,4-dimethoxyphenyl)-8-[(2R)-2-(3,4-dimethoxyphenyl)-5,7-dimethoxy-2H-chromen-3-yl]-5,7-dimethoxy-3,4-dihydro-2H-chromen-3-ol
• CAS: 1265882-02-7
• 化学式: C₃₈H₄₀O₁₁
• 分子量: 672.729
• InChiKey: OINCLNJNZAWJFM-XEHJOMOVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  49
• 可旋转键数：
  11
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  113
• 氢给体数：
  1
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  (2R)-3-[(2R,3S)-(5,7,3',4'-tetrakis(methyloxy)-3-hydroxyflavan-8-yl)]-5,7,3',4'-tetramethoxyflavan-3-ene 在 四氧化锇 、 N-甲基吗啉氧化物 作用下， 以 四氢呋喃 为溶剂， 以30%的产率得到(2S,3S)-3-[(2R,3S)-5,7,3',4'-tetrakis(methyloxy)-3-hydroxyflavan]-5,7,3',4'-tetrarnethoxyflavan-3-one
  参考文献：
  名称：

  Synthesis of C-3 Coupled Biflavonoids and C-3 Coupled Biflavonoid Analogues

  摘要：

  该发明涉及一种从起始物质或中间体中选择的光学不活性和光学活性化合物的制备方法，所述化合物选自C-3偶联的双黄酮类化合物和C-3偶联的双黄酮类似物，所述起始物质或中间体分别选自光学不活性或光学活性的黄酮-3-醇和光学活性的黄酮-3-酮，所述方法包括以下步骤：(a)提供具有黄酮-3-醇结构或为黄酮-3-酮的化合物，该化合物是光学不活性或活性的；(b)如果选择具有C-3碳上羟基的黄酮-3-醇结构化合物作为起始物质，则将具有黄酮-3-醇结构的化合物的C-3碳上的羟基转化为羟基，形成该化合物的黄酮-3-酮；(c)提供具有亲核芳香基团的化合物，所述化合物选自具有亲核芳香基团的化合物和具有黄酮类基本结构的化合物以及具有亲核芳香基团的化合物和不具有黄酮类基本结构的化合物；(d)在存在Lewis酸的情况下，将步骤(a)提供或步骤(b)获得的黄酮-3-酮与含有亲核芳香基团的化合物接触；(e)形成第一中间化合物，其中通过亲核加成使含有亲核芳香基团的化合物与黄酮-3-酮的C-3碳接触时，C-3碳上的羟基转化为羟基；(f)将第一中间化合物脱水，以在中间化合物的C-3碳和C-4碳之间引入双键，并同时去除C-3碳上的羟基，形成由亲核芳香基团取代C-3碳上的光学活性黄烯化合物；(g)可选地将所得的黄烯化合物经过氢硼氧化水合反应，从而去除C-3碳和C-4碳之间的双键，并同时在C-4碳引入羟基，形成第二中间化合物；(h)可选地进一步氧化步骤(g)中的第二中间化合物，将C-4碳上的羟基转化为羟基，从而形成在C-3碳上由所选亲核芳香基团取代的双黄酮或双黄酮类似物；(i)可选地，作为步骤(h)的替代，将步骤(f)中的所得黄烯化合物经过OsO4二羟基化反应，从而去除C-3碳和C-4碳之间的双键，并同时在C-4碳和C-3碳引入羟基，形成第三中间化合物；(j)将第三中间化合物脱水，从而去除C-3碳上的羟基，并在C-3碳和C-4碳之间引入双键，从而形成烯醇产物，并使该烯醇产物自发重排，形成在其C-4碳上具有羟基的双黄酮或双黄酮类似物，并在其C-3碳上由所选亲核芳香基团取代。

  公开号：

  US20120289715A1
• 作为产物：
  描述：

  (2R)-5,7,3',4'-tetramethoxyflavan-3-one 、 2alpha-(3,4-二甲氧基苯基)-5,7-二甲氧基-3,4-二氢-2H-1-苯并吡喃-3beta-醇 在 四氯化锡 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以10%的产率得到(2R)-3-[(2R,3S)-(5,7,3',4'-tetrakis(methyloxy)-3-hydroxyflavan-8-yl)]-5,7,3',4'-tetramethoxyflavan-3-ene
  参考文献：
  名称：

  Synthesis of C-3 Coupled Biflavonoids and C-3 Coupled Biflavonoid Analogues

  摘要：

  该发明涉及一种从起始物质或中间体中选择的光学不活性和光学活性化合物的制备方法，所述化合物选自C-3偶联的双黄酮类化合物和C-3偶联的双黄酮类似物，所述起始物质或中间体分别选自光学不活性或光学活性的黄酮-3-醇和光学活性的黄酮-3-酮，所述方法包括以下步骤：(a)提供具有黄酮-3-醇结构或为黄酮-3-酮的化合物，该化合物是光学不活性或活性的；(b)如果选择具有C-3碳上羟基的黄酮-3-醇结构化合物作为起始物质，则将具有黄酮-3-醇结构的化合物的C-3碳上的羟基转化为羟基，形成该化合物的黄酮-3-酮；(c)提供具有亲核芳香基团的化合物，所述化合物选自具有亲核芳香基团的化合物和具有黄酮类基本结构的化合物以及具有亲核芳香基团的化合物和不具有黄酮类基本结构的化合物；(d)在存在Lewis酸的情况下，将步骤(a)提供或步骤(b)获得的黄酮-3-酮与含有亲核芳香基团的化合物接触；(e)形成第一中间化合物，其中通过亲核加成使含有亲核芳香基团的化合物与黄酮-3-酮的C-3碳接触时，C-3碳上的羟基转化为羟基；(f)将第一中间化合物脱水，以在中间化合物的C-3碳和C-4碳之间引入双键，并同时去除C-3碳上的羟基，形成由亲核芳香基团取代C-3碳上的光学活性黄烯化合物；(g)可选地将所得的黄烯化合物经过氢硼氧化水合反应，从而去除C-3碳和C-4碳之间的双键，并同时在C-4碳引入羟基，形成第二中间化合物；(h)可选地进一步氧化步骤(g)中的第二中间化合物，将C-4碳上的羟基转化为羟基，从而形成在C-3碳上由所选亲核芳香基团取代的双黄酮或双黄酮类似物；(i)可选地，作为步骤(h)的替代，将步骤(f)中的所得黄烯化合物经过OsO4二羟基化反应，从而去除C-3碳和C-4碳之间的双键，并同时在C-4碳和C-3碳引入羟基，形成第三中间化合物；(j)将第三中间化合物脱水，从而去除C-3碳上的羟基，并在C-3碳和C-4碳之间引入双键，从而形成烯醇产物，并使该烯醇产物自发重排，形成在其C-4碳上具有羟基的双黄酮或双黄酮类似物，并在其C-3碳上由所选亲核芳香基团取代。

  公开号：

  US20120289715A1

文献信息

• [EN] SYNTHESIS OF C-3 COUPLED BIFLAVONOIDS AND C-3 COUPLED BIFLAVONOID ANALOGUES<br/>[FR] SYNTHÈSE DE BIFLAVONOÏDES COUPLÉS EN C-3 ET D'ANALOGUES DE BIFLAVONOÏDES COUPLÉS EN C-3
  申请人：UNIV FREE STATE ZA

  公开号：WO2011021167A1

  公开（公告）日：2011-02-24

  The invention relates to methods for the preparation of an optically inactive and optically active compounds which are selected from the group consisting of C-3 coupled biflavonoids and C-3 coupled biflavonoid analogues from a starting material or intermediate which are respectively selected from the group consisting of optically inactive or optically active flavan-3-ols and optically active flavan-3-ones, the method comprising the steps of (a) providing an optically inactive or active compound having a fIavan-3-ol structure or a compound which is a flavan-3-one, (b) if a compound having a flavan-3-ol structure with a hydroxy group on the C-3 carbon is selected as starting material, converting the hydroxy group on the C-3 carbon of the compound having the flavan-3-ol structure to an oxo group to form a flavan-3-one of that compound, (c) providing a compound having a nucleophilic aromatic moiety, which compound is selected from the group of compounds having a nucleophilic aromatic moiety and which have flavonoid base structures and compounds having a nucleophilic aromatic moiety and which do not have a flavonoid base structure, (d) contacting the flavan-3-one provided by step (a) or obtained by step (b) with the compound containing the nucleophilic aromatic moiety in the presence of a Lewis acid; (e) forming a first intermediate compound wherein the oxo group on the C-3 carbon is converted to a hydroxy group by virtue of nucleophilic addition when the compound containing the nucleophilic aromatic moiety is contacted to the C-3 carbon of the flavan-3-one, (f) subjecting the first intermediate compound to dehydration so as to introduce a double bond between the C-3 carbon and C-4 carbon of the intermediate compound with the concomitant removal of the hydroxy group from the C-3 carbon to form an optically active flavene compound which is substituted by the nucleophilic aromatic moiety on the C-3 carbon, (g) optionally subjecting the resultant flavene compound to hydroboration-oxidation hydration thereby removing said double bond between the C-3 carbon and the C-4 carbon with the concomitant introduction of a hydroxy group at the C-4 carbon to form a second intermediate compound, (h) further optionally oxidizing the second intermediate compound of step (g) thereby converting the hydroxy group at the said C-4 carbon to an oxo group, thereby forming a biflavonoid or biflavonoid analogue which is substituted by the selected nucleophilic aromatic moiety on the C-3 carbon, (ι) further optionally, and alternatively to step (h), subjecting the resultant flavene compound of step (f) to OsC4 dihydroxylation thereby removing said double bond between the C-3 carbon and C-4 carbon with the concomitant introduction of a hydroxy group at the C-4 carbon and a hydroxy group at the C-3 carbon to form a third intermediate compound, and (j) subjecting the third intermediate compound to dehydration whereby the hydroxy group at the C-3 carbon is removed and a double bond is introduced between the C-3 carbon and C-4 carbon thereby forming an enol product and allowing such enol product to rearrange spontaneously to form a biflavonoid or biflavonoid analogue having an oxo group at its C-4 carbon and which is substituted by the selected nucleophilic aromatic moiety on its C-3 carbon.

  该发明涉及从起始物质或中间体中选择的光学不活性和光学活性化合物的制备方法，所述化合物选自C-3偶联的双黄酮类和C-3偶联的双黄酮类类似物，所述起始物质或中间体分别选自光学不活性或光学活性的黄酮-3-醇和光学活性的黄酮-3-酮，所述方法包括以下步骤：(a)提供具有黄酮-3-醇结构或为黄酮-3-酮的化合物，该化合物是光学不活性或活性的；(b)如果选择具有C-3碳上羟基的黄酮-3-醇结构的化合物作为起始物质，则将该具有黄酮-3-醇结构的化合物上的C-3碳上的羟基转化为醛基，形成该化合物的黄酮-3-酮；(c)提供具有亲核芳香基团的化合物，所述化合物选自具有亲核芳香基团的化合物和具有黄酮基本结构的化合物以及具有亲核芳香基团的化合物和不具有黄酮基本结构的化合物；(d)在存在Lewis酸的情况下，将步骤(a)提供的或步骤(b)获得的黄酮-3-酮与含有亲核芳香基团的化合物接触；(e)形成第一中间化合物，其中通过亲核加成使含有亲核芳香基团的化合物与黄酮-3-酮的C-3碳接触时，C-3碳上的醛基转化为羟基；(f)将第一中间化合物脱水，以在中间化合物的C-3碳和C-4碳之间引入双键，并同时去除C-3碳上的羟基，形成一种在C-3碳上由亲核芳香基团取代的光学活性黄烯化合物；(g)可选地将所得的黄烯化合物经过氢硼氧化水合反应，从而去除C-3碳和C-4碳之间的双键，并同时在C-4碳引入羟基，形成第二中间化合物；(h)可选地进一步氧化步骤(g)中的第二中间化合物，从而将C-4碳上的羟基转化为醛基，形成在C-3碳上由选定的亲核芳香基团取代的双黄酮或双黄酮类似物；(ι)可选地，作为步骤(h)的替代，将步骤(f)中的所得黄烯化合物经过OsC4双羟基化反应，从而去除C-3碳和C-4碳之间的双键，并同时在C-4碳和C-3碳引入羟基，形成第三中间化合物；(j)将第三中间化合物脱水，从而去除C-3碳上的羟基，并在C-3碳和C-4碳之间引入双键，形成烯醇产物，并使该烯醇产物自发重排，形成在其C-4碳上具有醛基且在其C-3碳上由选定的亲核芳香基团取代的双黄酮或双黄酮类似物。
• US9296717B2
  申请人：——

  公开号：US9296717B2

  公开（公告）日：2016-03-29
• Synthesis of C-3 Coupled Biflavonoids and C-3 Coupled Biflavonoid Analogues
  申请人：Van Der Westhuizen Jan Hendrik

  公开号：US20120289715A1

  公开（公告）日：2012-11-15

  The invention relates to methods for the preparation of an optically inactive and optically active compounds which are selected from the group consisting of C-3 coupled biflavonoids and C-3 coupled biflavonoid analogues from a starting material or intermediate which are respectively selected from the group consisting of optically inactive or optically active flavan-3-ols and optically active flavan-3-ones, the method comprising the steps of (a) providing an optically inactive or active compound having a flavan-3-ol structure or a compound which is a flavan-3-one, (b) if a compound having a flavan-3-ol structure with a hydroxy group on the C-3 carbon is selected as starting material, converting the hydroxy group on the C-3 carbon of the compound having the flavan-3-ol structure to an oxo group to form a flavan-3-one of that compound, (c) providing a compound having a nucleophilic aromatic moiety, which compound is selected from the group of compounds having a nucleophilic aromatic moiety and which have flavonoid base structures and compounds having a nucleophilic aromatic moiety and which do not have a flavonoid base structure, (d) contacting the flavan-3-one provided by step (a) or obtained by step (b) with the compound containing the nucleophilic aromatic moiety in the presence of a Lewis acid; (e) forming a first intermediate compound wherein the oxo group on the C-3 carbon is converted to a hydroxy group by virtue of nucleophilic addition when the compound containing the nucleophilic aromatic moiety is contacted to the C-3 carbon of the flavan-3-one, (f) subjecting the first intermediate compound to dehydration so as to introduce a double bond between the C-3 carbon and C-4 carbon of the intermediate compound with the concomitant removal of the hydroxy group from the C-3 carbon to form an optically active flavene compound which is substituted by the nucleophilic aromatic moiety on the C-3 carbon, (g) optionally subjecting the resultant flavene compound to hydroboration-oxidation hydration thereby removing said double bond between the C-3 carbon and the C-4 carbon with the concomitant introduction of a hydroxy group at the C-4 carbon to form a second intermediate compound, (h) further optionally oxidizing the second intermediate compound of step (g) thereby converting the hydroxy group at the said C-4 carbon to an oxo group, thereby forming a biflavonoid or biflavonoid analogue which is substituted by the selected nucleophilic aromatic moiety on the C-3 carbon, (i) further optionally, and alternatively to step (h), subjecting the resultant flavene compound of step (f) to OsO 4 dihydroxylation thereby removing said double bond between the C-3 carbon and C-4 carbon with the concomitant introduction of a hydroxy group at the C-4 carbon and a hydroxy group at the C-3 carbon to form a third intermediate compound, and (j) subjecting the third intermediate compound to dehydration whereby the hydroxy group at the C-3 carbon is removed and a double bond is introduced between the C-3 carbon and C-4 carbon thereby forming an enol product and allowing such enol product to rearrange spontaneously to form a biflavonoid or biflavonoid analogue having an oxo group at its C-4 carbon and which is substituted by the selected nucleophilic aromatic moiety on its C-3 carbon.

  该发明涉及一种从起始物质或中间体中选择的光学不活性和光学活性化合物的制备方法，所述化合物选自C-3偶联的双黄酮类化合物和C-3偶联的双黄酮类似物，所述起始物质或中间体分别选自光学不活性或光学活性的黄酮-3-醇和光学活性的黄酮-3-酮，所述方法包括以下步骤：(a)提供具有黄酮-3-醇结构或为黄酮-3-酮的化合物，该化合物是光学不活性或活性的；(b)如果选择具有C-3碳上羟基的黄酮-3-醇结构化合物作为起始物质，则将具有黄酮-3-醇结构的化合物的C-3碳上的羟基转化为羟基，形成该化合物的黄酮-3-酮；(c)提供具有亲核芳香基团的化合物，所述化合物选自具有亲核芳香基团的化合物和具有黄酮类基本结构的化合物以及具有亲核芳香基团的化合物和不具有黄酮类基本结构的化合物；(d)在存在Lewis酸的情况下，将步骤(a)提供或步骤(b)获得的黄酮-3-酮与含有亲核芳香基团的化合物接触；(e)形成第一中间化合物，其中通过亲核加成使含有亲核芳香基团的化合物与黄酮-3-酮的C-3碳接触时，C-3碳上的羟基转化为羟基；(f)将第一中间化合物脱水，以在中间化合物的C-3碳和C-4碳之间引入双键，并同时去除C-3碳上的羟基，形成由亲核芳香基团取代C-3碳上的光学活性黄烯化合物；(g)可选地将所得的黄烯化合物经过氢硼氧化水合反应，从而去除C-3碳和C-4碳之间的双键，并同时在C-4碳引入羟基，形成第二中间化合物；(h)可选地进一步氧化步骤(g)中的第二中间化合物，将C-4碳上的羟基转化为羟基，从而形成在C-3碳上由所选亲核芳香基团取代的双黄酮或双黄酮类似物；(i)可选地，作为步骤(h)的替代，将步骤(f)中的所得黄烯化合物经过OsO4二羟基化反应，从而去除C-3碳和C-4碳之间的双键，并同时在C-4碳和C-3碳引入羟基，形成第三中间化合物；(j)将第三中间化合物脱水，从而去除C-3碳上的羟基，并在C-3碳和C-4碳之间引入双键，从而形成烯醇产物，并使该烯醇产物自发重排，形成在其C-4碳上具有羟基的双黄酮或双黄酮类似物，并在其C-3碳上由所选亲核芳香基团取代。