(3S,3aR,8bS)-(-)-2,3,3a,8b-Tetrahydro-3-hydroxy-3,3a,6,8b-tetramethyl-1H-cyclopentabenzofuran | 154800-88-1

• 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: (3S,3aR,8bS)-(-)-2,3,3a,8b-Tetrahydro-3-hydroxy-3,3a,6,8b-tetramethyl-1H-cyclopentabenzofuran
• 英文别名: 3α-hydroxydebromoaplysin；(3S,3aR,8bS)-2,3,3a,8b-tetrahydro-3-hydroxy-3,3a,6,8b-tetramethyl-1H-cyclopenta[b]benzofuran；(3S,3aR,8bS)-3,3a,6,8b-tetramethyl-1,2-dihydrocyclopenta[b][1]benzofuran-3-ol
• CAS: 154800-88-1
• 化学式: C₁₅H₂₀O₂
• 分子量: 232.323
• InChiKey: UUTNFVHOXZVUMX-SOUVJXGZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3S,3aR,8bS)-(-)-2,3,3a,8b-Tetrahydro-3-hydroxy-3,3a,6,8b-tetramethyl-1H-cyclopentabenzofuran 在 platinum(IV) oxide 吡啶 、 氢气 、 三氯氧磷 作用下， 以 乙醇 为溶剂， 反应 21.0h， 生成 debromoaplysin
  参考文献：
  名称：

  A remarkable substituent effect on the enantioselectivity of tandem asymmetric epoxidation and enantiospecific ring expansion of cyclopropylidene alcohols: a new enantiocontrolled synthesis of (-)-debromoaplysin and (-)-aplysin

  摘要：

  A remarkable substituent effect by the tert-butyldimethylsiloxy group on the enantioselectivity of the tandem asymmetric epoxidation and enantiospecific ring expansion of 2-[2-(tert-butyldimethylsiloxy)-4-methylphenyl]-2-cyclopropylideneethanol (18), affording (S)-(-)-2-[2-(tert-butyldimethylsiloxy)-4-methylphenyl]-2-hydroxymethylcyclobutanone (21) in high yield and high enantiomeric excess, was observed. This enabled us to accomplish a concise and highly enantioselective total synthesis of (-)-debromoaplysin (2) and (-)-aplysin (1), providing a new and general strategy for the enantioselective synthesis of biologically important substances having the dihydrobenzofuran framework.

  DOI：

  10.1021/jo00080a014
• 作为产物：
  描述：

  (3R)-3-<2-(tert-Butyldimethylsiloxy)-4-methylphenyl>-1,3-dimethyl-2-methylidenecyclopentanol 在 四丁基氟化铵 、 mercury(II) trifluoroacetate 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 生成 (3S,3aR,8bS)-(-)-2,3,3a,8b-Tetrahydro-3-hydroxy-3,3a,6,8b-tetramethyl-1H-cyclopentabenzofuran
  参考文献：
  名称：

  A remarkable substituent effect on the enantioselectivity of tandem asymmetric epoxidation and enantiospecific ring expansion of cyclopropylidene alcohols: a new enantiocontrolled synthesis of (-)-debromoaplysin and (-)-aplysin

  摘要：

  A remarkable substituent effect by the tert-butyldimethylsiloxy group on the enantioselectivity of the tandem asymmetric epoxidation and enantiospecific ring expansion of 2-[2-(tert-butyldimethylsiloxy)-4-methylphenyl]-2-cyclopropylideneethanol (18), affording (S)-(-)-2-[2-(tert-butyldimethylsiloxy)-4-methylphenyl]-2-hydroxymethylcyclobutanone (21) in high yield and high enantiomeric excess, was observed. This enabled us to accomplish a concise and highly enantioselective total synthesis of (-)-debromoaplysin (2) and (-)-aplysin (1), providing a new and general strategy for the enantioselective synthesis of biologically important substances having the dihydrobenzofuran framework.

  DOI：

  10.1021/jo00080a014

文献信息

• Enantioselective formal total synthesis of aplysin utilizing a palladium-catalyzed addition of an arylboronic acid to an allenic alcohol—Eschenmoser/Claisen rearrangement
  作者：Masahiro Yoshida、Yasunobu Shoji、Kozo Shishido

  DOI：10.1016/j.tet.2010.04.134

  日期：2010.7

  The enantioselective formal total synthesis of aplysin has been achieved utilizing a palladium-catalyzed addition of arylboronic acid to the allenic alcohol followed by the Eschenmoser/Claisen rearrangement as the key steps.

  使用钯催化的芳基硼酸加成到烯丙醇中，然后进行Eschenmoser / Claisen重排，这是关键步骤，从而实现了对aplysin的对映选择性正式全合成。
• A remarkable substituent effect on the enantioselectivity of tandem asymmetric epoxidation and enantiospecific ring expansion of cyclopropylidene alcohols: a new enantiocontrolled synthesis of (-)-debromoaplysin and (-)-aplysin
  作者：Hideo Nemoto、Masatoshi Nagamochi、Hiroki Ishibashi、Keiichiro Fukumoto

  DOI：10.1021/jo00080a014

  日期：1994.1

  A remarkable substituent effect by the tert-butyldimethylsiloxy group on the enantioselectivity of the tandem asymmetric epoxidation and enantiospecific ring expansion of 2-[2-(tert-butyldimethylsiloxy)-4-methylphenyl]-2-cyclopropylideneethanol (18), affording (S)-(-)-2-[2-(tert-butyldimethylsiloxy)-4-methylphenyl]-2-hydroxymethylcyclobutanone (21) in high yield and high enantiomeric excess, was observed. This enabled us to accomplish a concise and highly enantioselective total synthesis of (-)-debromoaplysin (2) and (-)-aplysin (1), providing a new and general strategy for the enantioselective synthesis of biologically important substances having the dihydrobenzofuran framework.