rac-(1R,4aR,9bS)-2,3,4a,9b-tetrahydro-7,9-dimethoxy-1-(1-methylethyl)-4(1H)-dibenzofuranone

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 香豆素
• 英文名称: rac-(1R,4aR,9bS)-2,3,4a,9b-tetrahydro-7,9-dimethoxy-1-(1-methylethyl)-4(1H)-dibenzofuranone
• 英文别名: rel-(1R,4aR,9bS)-2,3,4a,9b-tetrahydro-7,9-dimethoxy-1-(1-methylethyl)-4(1H)-dibenzofuranone；rac-(1R,4aR,9bS)-7,9-dimethoxy-1-(1-methylethyl)-1,2,3,4,4a,9b-hexahydrodibenzofuran-4-one；(1R*,5aR*,9bS*)-7,9-dimethoxy-1-(1-methylethyl)-1,2,3,4,4a,9b-hexahydrodibenzofuran-4-one；(1R,4aR,9bS)-7,9-dimethoxy-1-propan-2-yl-2,3,4a,9b-tetrahydro-1H-dibenzofuran-4-one
• 化学式: C₁₇H₂₂O₄
• 分子量: 290.359
• InChiKey: IZTCOACBQSCIQV-PJQXDXOGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 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：

  rac-(1R,4aR,9bS)-2,3,4a,9b-tetrahydro-7,9-dimethoxy-1-(1-methylethyl)-4(1H)-dibenzofuranone 在 4-二甲氨基吡啶 、 四氧化锇 、 正丁基锂 、 N-甲基吗啉氧化物 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 75.5h， 生成 (1R,4S,4aR,9bS)-7,9-dimethoxy-1-(1-methylethyl)-1,2,3,4,4a,9b-hexahydrodibenzofuran-4-spiro-4'-dioxolan-2'-one
  参考文献：
  名称：

  Asymmetric Total Synthesis of (−)-Linderol A

  摘要：

  The first asymmetric total synthesis of (-)-Linderol A, a potent inhibitor of melanin biosynthesis of cultured B-16 melanoma cells, has been achieved via two key reactions: a diastereoselective [2+2] photocycloaddition of a coumarin-3-carboxylate bearing a chiral auxiliary with 3-methyl-1-butene and a subsequent stereoconvergent transformation of the photoadducts with use of dimethylsulfoxonium methylide to afford a tetrahydrodibenzofuran derivative.

  DOI：

  10.1021/jo070682+
• 作为产物：
  描述：

  3-benzyloxycarbonyl-5,7-dimethoxycoumarin 在 palladium on activated charcoal 氢气 作用下， 以 乙酸乙酯 、 N,N-二甲基甲酰胺 、 xylene 、 苯 为溶剂， 反应 49.0h， 生成 rac-(1R,4aR,9bS)-2,3,4a,9b-tetrahydro-7,9-dimethoxy-1-(1-methylethyl)-4(1H)-dibenzofuranone
  参考文献：
  名称：

  Improved Synthesis of (±)-Linderol A and Its First Conversion to (±)- 6-epi-Adunctin E

  摘要：

  DOI：

  10.3987/com-05-10345

文献信息

• The First Total Synthesis of (±)-Linderol A, a Tricyclic Hexahydrodibenzofuran Constituent of <i>Lindera umbellata</i> Bark, with Potent Inhibitory Activity on Melanin Biosynthesis of Cultured B-16 Melanoma Cells
  作者：Masayuki Yamashita、Nobukazu Ohta、Ikuo Kawasaki、Shunsaku Ohta

  DOI：10.1021/ol0157398

  日期：2001.5.1

  [reaction in text] The first total synthesis of (+/-)-linderol A, a hexahydrodibenzofuran isolated from Lindera umbellata bark, with potent inhibitory activity on melanin biosynthesis of cultured B-16 melanoma cells was achieved via a 20-step of reaction in 7.64% overall yield starting from 4,6-dimethoxysalicylaldehyde.

  [文本中的反应]通过20个步骤的反应，首次合成了（+/-）-林德洛尔A，这是一种从伞形树皮中分离出来的六氢二苯并呋喃，对培养的B-16黑色素瘤细胞的黑色素生物合成具有有效的抑制活性。从4，6-二甲氧基水杨醛开始，总收率为7.64％。
• Novel stereoconvergent transformation of 1,2a-disubstituted 1,2,2a,8b-tetrahydro-3H-benzo[b]cyclobuta[d]pyran-3-ones to 1,3-disubstituted 1,2,4a,9b-tetrahydrodibenzofuran-4-ols and its application to the second-generation synthesis of (±)-linderol A
  作者：Masayuki Yamashita、Tomoki Inaba、Masaki Nagahama、Takashi Shimizu、Sachiko Kosaka、Ikuo Kawasaki、Shunsaku Ohta

  DOI：10.1039/b503890a

  日期：——

  1,2a-Disubstituted 1,2,2a,8b-tetrahydro-3H-benzo[b]cyclobuta[d]pyran-3-ones bearing an electron-withdrawing group at the 2a-position were treated with two equivalents of dimethylsulfoxonium methylide to give r-1,t-4a,t-9b-1,3-disubstituted 1,2,4a,9b-tetrahydrodibenzofuran-4-ols stereoconvergently regardless of the stereochemistry of the 1-position on the benzocyclobutapyran ring. This methodology was

  用两当量的二甲基亚砜基亚砜处理在2a位带有吸电子基团的1,2a-二取代的1,2,2a，8b-四氢-3H-苯并[b]环丁[d]吡喃-3-酮不管苯并环丁吡喃环上1-位的立体化学如何，均一地聚合给出r-1，t-4a，t-9b-1,3-二取代的1,2,4a，9b-四氢二苯并呋喃-4-醇。该方法学被用于（+/-）-linderol A的第二代合成，这是一种抑制黑色素的生物合成天然产物。
• First Total Synthesis of (±)-Linderol A, a Tricyclic Hexahydrodibenzofuran Constituent of <i>Lindera umbellata</i> Bark, with Potent Inhibitory Activity on Melanin Biosynthesis of Cultured B-16 Melanoma Cells
  作者：Masayuki Yamashita、Nobukazu Ohta、Takashi Shimizu、Kayoko Matsumoto、Yoko Matsuura、Ikuo Kawasaki、Tetsuaki Tanaka、Naoyoshi Maezaki、Shunsaku Ohta

  DOI：10.1021/jo020619e

  日期：2003.2.1

  The first total synthesis of (+/-)-Linderol A, a hexahydrodibenzofuran constituent of Lindera umbellata bark, with potent inhibitory activity on the melanin biosynthesis of cultured B-16 melanoma cells, was achieved through 19 steps of reaction in 6.6% overall yield, in which the critical step was a tandem reaction of a 3-ethoxycarbonylcoumarin derivative with dimethylsulfoxonium methylide to yield the 2-ethoxycarbonylcyclopenta[b]benzofuran-3-ol derivative.
• Discrepancy of the spectral data between adunctin E and the synthetic one
  作者：Masayuki Yamashita、Navnath Dnyanoba Yadav、Yuto Sumida、Ikuo Kawasaki、Ai Kurume、Shunsaku Ohta

  DOI：10.1016/j.tetlet.2007.06.050

  日期：2007.8

  Compound (2), which has been proposed as the structure of adunctin E (1), was prepared in nine steps in 17% overall yield from hexahydrodibenzofuranone (4); however, the spectral data of this compound, including H-1 and C-13 NMR spectra, were inconsistent with the literature data for adunctin E (1). Thus, we suggest that the proposed structure for adunctin E or the reported NMR spectral data was incorrect. (c) 2007 Elsevier Ltd. All rights reserved.
• Improved Synthesis of (±)-Linderol A and Its First Conversion to (±)- 6-epi-Adunctin E
  作者：Shunsaku Ohta、Masayuki Yamashita、Takashi Shimizu、Tomoki Inaba、Ai Takada、Ikuko Takao、Ikuo Kawasaki

  DOI：10.3987/com-05-10345

  日期：——