(±)-二氢-4-[[3-甲氧基-4-(苯基甲氧基)苯基]甲基]-2(3H)-呋喃酮 | 92831-74-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 中文名称: (±)-二氢-4-[[3-甲氧基-4-(苯基甲氧基)苯基]甲基]-2(3H)-呋喃酮
• 英文名称: 4-<<4-(benzyloxy)-3-methoxyphenyl>methyl>dihydro-2(3H)-furanone
• 英文别名: (+/-)-β-(4-benzyloxy-3-methoxybenzyl)-γ-butyrolactone；4-[3-methoxy-(4-phenylmethoxy)phenylmethyl]dihydrofuran-2-one；rac-4-[4-(benzyloxy)-3-methoxybenzyl]tetrahydrofuran-2-one；(benzyloxy-4 methoxy-3 benzyl)-4 dihydro-3H-furannone-2；3-((4-benzyloxy-3-methoxy)benzyl)butanolide；Dihydro-4-[[3-methoxy-4-(phenylmethoxy)phenyl]methyl]-2(3H)-furanone；4-[(3-methoxy-4-phenylmethoxyphenyl)methyl]oxolan-2-one
• CAS: 92831-74-8
• 化学式: C₁₉H₂₀O₄
• 分子量: 312.365
• InChiKey: FKRJBUYHQOXRCE-UHFFFAOYSA-N

物化性质

• 沸点：
  493.6±30.0 °C(Predicted)
• 密度：
  1.186±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (±)-二氢-4-[[3-甲氧基-4-(苯基甲氧基)苯基]甲基]-2(3H)-呋喃酮 在 palladium on activated charcoal 咪唑 、 四丁基氟化铵 、 氢气 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 六甲基磷酰三胺 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.08h， 生成 dihydrovanillylsyringyl-2(3H)-furanone
  参考文献：
  名称：

  Biosynthesis of yatein in Anthriscus sylvestrisA part of this work was performed as a part of the R & D Project of Industrial Science and Technology Frontier Program supported by NEDO (New Energy and Industrial Technology Development Organization).

  摘要：

  尽管 yatein 作为典型心材木质素和抗肿瘤木质素 podophyllotoxin 的关键生物合成中间体具有重要性，但其生物合成机制知之甚少。本研究基于对 Anthriscus sylvestris 单独施用 [13C]苯丙氨酸和重氢标记的木质素，以及同时施用两种不同的重氢标记木质素，建立了从 matairesinol 出发的两条独立分支路径，一条通过 thujaplicatin、5-甲基 thujaplicatin 和 4,5-二甲基 thujaplicatin 合成 yatein，另一条通过 pluviatolide 合成 bursehernin。后一条路径并未通向 yatein，排除了 matairesinol 到 yatein 的代谢网络的存在。

  DOI：

  10.1039/b304411d
• 作为产物：
  描述：

  4-苄氧基-3-甲氧基苯甲醛 在 偶氮二异丁腈 N-溴代丁二酰亚胺(NBS) 、 lithium aluminium tetrahydride 、 jones reagent 、 三丁基氯化锡 、 sodium hydride 、 sodium cyanoborohydride 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 水 、 叔丁醇 为溶剂， 生成 (±)-二氢-4-[[3-甲氧基-4-(苯基甲氧基)苯基]甲基]-2(3H)-呋喃酮
  参考文献：
  名称：

  基于自由基循环的木脂素方法。4-芳基甲基二氢呋喃-2-酮的合成

  摘要：

  从相应的苯甲醛中获得的肉桂醇 7a-d 的溴缩醛化生成了溴缩醛 10a-d。溴缩醛 10a-d 的 5-exo trig 自由基环化，然后对所得环状缩醛 11a-d 进行一步水解-氧化，分别提供了标题化合物 6a-d，它们是各种木脂素的成熟中间体。

  DOI：

  10.1081/scc-100104837

文献信息

• Enantioselective Lignan Synthesis by Cell-free Extracts of<i>Forsythia koreana</i>
  作者：Toshiaki Umezawa、Hiroyuki Kuroda、Toshinari Isohata、Takayoshi Higuchi、Mikio Shimada

  DOI：10.1271/bbb.58.230

  日期：1994.1

  The Forsythia koreana plant produces such lignans as ( − )-secoisolariciresinol, and ( + )-pinoresinol. Cell-free extracts from the plant catalyzed the enantioselective formation of ( − )-[2H10]secoisolariciresinol from [9, 9-2H2, OC2H3]coniferyl alcohol in the presence of NADPH and H2 O2. On the other hand, [2H10]lariciresinosl isolated from the enzymatic reaction products was found to be predominantly composed of the unnatural ( − )-enantiomer [88% enantiomer excess (e.e.)]. The stereoselectivity for the formation of these lignans can be explained, at least in part, by the finding that the enzyme system also catalyzed the stereoselective reduction of ( + )-lariciresinol, but not its ( − )-enantiomer, to ( − )-secoisolariciresinol.

  韩国连翘植物产生的木酚类物质包括（−）-半紫葳醇和（+）-松脂醇。来自这种植物的无细胞提取物在NADPH和H2O2存在下催化了（−）-[2H10]半紫葳醇从[9,9-2H2,OC2H3]香豆醇的对映选择性形成。另一方面，从酶促反应产物中分离出来的[2H10]拉里醇主要由不自然的（−）-对映体构成，具有88%的对映体超量（e.e.）。这些木酚类物质形成的立体选择性部分可以通过发现该酶系统也催化（+）-拉里醇的立体选择性还原，但不催化其（−）-对映体，形成（−）-半紫葳醇来解释。
• RADICAL CYCLISATION BASED APPROACH TO LIGNANS. SYNTHESIS OF 4-ARYLMETHYLDIHYDROFURAN-2-ONES
  作者：A. Srikrishna、S. Danieldoss

  DOI：10.1081/scc-100104837

  日期：2001.1

  Bromoacetalisation of the cinnamyl alcohols 7a–d, obtained from the corresponding benzaldehydes, generated the bromoacetals 10a–d. The 5-exo trig radical cyclisation of the bromoacetals 10a–d followed by one step hydrolysis-oxidation of the resulting cyclic acetals 11a–d furnished the title compounds 6a–d, respectively, well-established intermediates of a variety of lignans.

  从相应的苯甲醛中获得的肉桂醇 7a-d 的溴缩醛化生成了溴缩醛 10a-d。溴缩醛 10a-d 的 5-exo trig 自由基环化，然后对所得环状缩醛 11a-d 进行一步水解-氧化，分别提供了标题化合物 6a-d，它们是各种木脂素的成熟中间体。
• Intramolecular Regioselective Insertion into Unactivated Prochiral Carbon−Hydrogen Bonds with Diazoacetates of Primary Alcohols Catalyzed by Chiral Dirhodium(II) Carboxamidates. Highly Enantioselective Total Synthesis of Natural Lignan Lactones
  作者：Jeffrey W. Bode、Michael P. Doyle、Marina N. Protopopova、Qi-Lin Zhou

  DOI：10.1021/jo961607u

  日期：1996.1.1

  Intramolecular insertion into unactivated prochiral C-H bonds of 3-aryl-1-propyl diazoacetates catalyzed by dirhodium(II) tetrakis[methyl 1-(3-phenyl propanoyl)imidazolidin-2-one-4(R or S)-carboxylate], Rh-2(4R-MPPIM)(4) or Rh-2(4S-MPPIM)(4), occurs in 91-96% ee and with virtually complete regiocontrol for the formation of beta-benzyl-gamma-butyrolactones. This methodology has been applied to the total synthesis of dibenzylbutyrolactone lignans (-)- and (+)-enterolactone, (-)- and (+)-hinokinin, and (+)-arctigenin from substituted cinnamic acids in 19-27% overall yields. Aryltetralin lignan (+)-isodeoxypodophyllotoxin was prepared from the reactant 3,4-(methylenedioxy)cinnamic acid in 36% yield overall, and the lactone precursor to (+)-isolauricerisinol was formed in 96.5% ee and 23% yield overall. Applications of the chiral Rh-2(MPPIM)4 catalysts to fully aliphatic systems resulting in the formation of beta-substituted-gamma-butyrolactones with high regiocontrol and with 93-96% ee have demonstrated the generality of this methodology. A model that provides accurate predictions of beta-substituted-gamma-butyrolactone absolute configurations in these asymmetric metal carbene transformations is described.
• Loriot; Thomas; Brown, Bulletin de la Societe Chimique de France, 1985, vol. NO. 5, # 5, p. 871 - 875
  作者：Loriot、Thomas、Brown

  DOI：——

  日期：——
• Biosynthesis of yatein in Anthriscus sylvestrisA part of this work was performed as a part of the R &amp; D Project of Industrial Science and Technology Frontier Program supported by NEDO (New Energy and Industrial Technology Development Organization).
  作者：Norikazu Sakakibara、Shiro Suzuki、Toshiaki Umezawa、Mikio Shimada

  DOI：10.1039/b304411d

  日期：——

  Little is known about the biosynthesis of yatein, in spite of its importance as a typical heartwood lignan and a key biosynthetic intermediate of the antitumor lignan podophyllotoxin. The present study, based on individual administration of [13C]phenylalanine and deuterium labelled lignans and simultaneous administration of two distinct lignans labelled with deuterium atoms to Anthriscus sylvestris, established the two independent branch pathways from matairesinol, one to afford yatein via thujaplicatin, 5-methylthujaplicatin, and 4,5-dimethylthujaplicatin and the other to bursehernin via pluviatolide. The latter pathway did not lead to yatein, eliminating the presence of a metabolic grid from matairesinol to yatein.

  尽管 yatein 作为典型心材木质素和抗肿瘤木质素 podophyllotoxin 的关键生物合成中间体具有重要性，但其生物合成机制知之甚少。本研究基于对 Anthriscus sylvestris 单独施用 [13C]苯丙氨酸和重氢标记的木质素，以及同时施用两种不同的重氢标记木质素，建立了从 matairesinol 出发的两条独立分支路径，一条通过 thujaplicatin、5-甲基 thujaplicatin 和 4,5-二甲基 thujaplicatin 合成 yatein，另一条通过 pluviatolide 合成 bursehernin。后一条路径并未通向 yatein，排除了 matairesinol 到 yatein 的代谢网络的存在。