2',7-二羟基-4'-甲氧基异黄烷 | 20879-05-4

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 异黄酮类化合物
• 中文名称: 2',7-二羟基-4'-甲氧基异黄烷
• 英文名称: vestitol
• 英文别名: (3S)-vestitol；(+)-Vestitol；(3S)-3-(2-hydroxy-4-methoxyphenyl)-3,4-dihydro-2H-chromen-7-ol
• CAS: 20879-05-4
• 化学式: C₁₆H₁₆O₄
• 分子量: 272.301
• InChiKey: XRVFNNUXNVWYTI-LLVKDONJSA-N

物化性质

• 熔点：
  156 °C
• 沸点：
  418.5±45.0 °C(Predicted)
• 密度：
  1.282±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

安全信息

• 海关编码：
  2932999099

反应信息

• 作为反应物：
  描述：

  2',7-二羟基-4'-甲氧基异黄烷 在 盐酸 作用下， 以 乙醇 为溶剂， 反应 20.0h， 生成
  参考文献：
  名称：

  Bezuidenhoudt, Barend C. B.; Brandt, Edward V.; Roux, David G., Journal of the Chemical Society. Perkin transactions I, 1984, p. 2767 - 2778

  摘要：

  DOI：
• 作为产物：
  描述：

  (6aR,11alphaR)-rel-6alpha,11alpha-二氢-9-甲氧基-6H-苯并呋喃并[3,2-c][1]苯并吡喃-3-醇 在 sodium cyanoborohydride 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以85%的产率得到2',7-二羟基-4'-甲氧基异黄烷
  参考文献：
  名称：

  Oligomeric isoflavonoids. Part 4.† Synthesis of the daljanelin class of isoflavonoid–neoflavonoid dimers

  摘要：

  将亲电子 C1 片段引入到紫檀核中，然后进行 C6-C2 苯并呋喃类前体的阴离子偶联，最后引入最终的 C6 片段的方案，允许合成 daljanelins B 3 和 D 5。还证明了与紫檀素部分的 C-2 具有相同的亲电子 C1 片段以获得 daljanelin A 2 的前体。

  DOI：

  10.1039/a904944d

文献信息

• 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。
• Synthetic access to optically active isoflavans by using allylic substitution
  作者：Yuji Takashima、Yuki Kaneko、Yuichi Kobayashi

  DOI：10.1016/j.tet.2009.10.116

  日期：2010.1

  A general approach to the (S)- and (R)-isoflavans was invented, and efficiency of the method was demonstrated by the synthesis of (S)-equol ((S)-3), (R)-sativan ((R)-4), and (R)-vestitol ((R)-5). The key step is the allylic substitution of (S)-6a (Ar1=2,4-(MeO)2C6H3) and (R)-6b (Ar1=2,4-(BnO)2C6H3) with copper reagents derived from CuBr·Me2S and Ar2-MgBr (7a, Ar2=4-MeOC6H4; 7b, 2,4-(MeO)2C6H3; 7c,

  发明了（S）-和（R）-异黄酮的通用方法，并且该方法的效率通过合成（S）-雌马酚（（S）-3），（R）-sativan（（R）-4），和（R）-vestitol（（R）-5）。关键的步骤是（的烯丙基取代小号） - 6a中（AR 1 = 2,4-（MEO）2 C ^ 6 ħ 3）和（- [R ）-图6b（AR 1 = 2,4-（BNO）2 Ç6 H 3）和衍生自CuBr·Me 2 S和Ar 2 -MgBr（7a，Ar 2 = 4-MeOC 6 H 4 ; 7b，2,4-（MeO）2 C 6 H 3 ; 7c，2的铜试剂-momo -4- MeOC 6 ħ 3），家具抗小号ñ 2的产品（[R ）-图8a和（小号） - 8b中，ç93-97％的手性转移，收率为60-75％。产物的烯烃部分被氧化裂解，然后除去Ar 1部分上的Me和Bn基团。最后，用K 2 CO 3和Mitsunobu试剂对溴化苯酚
• A general asymmetric route to enantio-enriched isoflavanes via an organocatalytic annulation of o-quinone methides and aldehydes
  作者：Jian Zhang、Shuangzhan Zhang、Huixin Yang、Ding Zhou、Xueting Yu、Wei Wang、Hexin Xie

  DOI：10.1016/j.tetlet.2018.05.016

  日期：2018.6

  Reported herein is a general approach to optically active isoflavanes based on a chiral amine-catalyzed [4 + 2] asymmetric annulation of o-quinone methides and aldehydes. A number of naturally occurring isoflavanes, including equol, sativan, isosativan, vestitol and medicarpin, as well as isoflavane analogues were readily prepared with good to excellent enantioselectivities.

  本文报道的是基于手性胺催化的邻醌甲基化物和醛的[4 + 2]不对称环空的旋光异黄酮的一般方法。易于制备具有良好至优异对映选择性的许多天然存在的异黄酮，包括雌马酚，sativan，isosativan，vestitol和medicarpin，以及异黄烷类似物。
• US9296717B2
  申请人：——

  公开号：US9296717B2

  公开（公告）日：2016-03-29
• Bezuidenhoudt, Barend C. B.; Brandt, Edward V.; Roux, David G., Journal of the Chemical Society. Perkin transactions I, 1984, p. 2767 - 2778
  作者：Bezuidenhoudt, Barend C. B.、Brandt, Edward V.、Roux, David G.

  DOI：——

  日期：——