(+/-)-12-Noralliacolide | 79232-31-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (+/-)-12-Noralliacolide
• 英文别名: (1S,5S,8R,9R,11R)-5-hydroxy-8,12,12-trimethyl-2,10-dioxatetracyclo[7.4.0.01,5.09,11]tridecan-3-one
• CAS: 79232-31-8；122743-34-4；122743-35-5
• 化学式: C₁₄H₂₀O₄
• 分子量: 252.31
• InChiKey: DTNFWWBECYJQMT-YWIKUWRNSA-N

物化性质

• 沸点：
  433.2±45.0 °C(Predicted)
• 密度：
  1.29±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  59.1
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (+/-)-12-Noralliacolide 在 palladium on activated charcoal 2,2,6,6-tetramethylpiperidinyl-lithium 、 氢气 作用下， 以 四氢呋喃 、 甲醇 、 六甲基磷酰三胺 、 正己烷 为溶剂， -20.0~25.0 ℃ 、206.84 kPa 条件下， 反应 15.5h， 生成 alliacolide
  参考文献：
  名称：

  A Stereoselective Total Synthesis of (.+-.)-Alliacol A and Congeners of Marasmius Alliaceus

  摘要：

  Synthesis of alliacolide(1), alliacol A (2), and 12-noralliacolide (4), members of the alliacane family of sesquiterpene lactones, was accomplished through both syn- and anti-modes of intramolecular S-N' displacement. Two routes to 12-noralliacolide (4) are presented, which contrast brevity and efficiency in stereoselection (i.e. 14 --> 16/17 versus 37a/b --> 38). Since both routes culminate in C-ring annulation, introduction of the correct stereochemical arrangement relied heavily on the structural features of the hydrindane (AB) precursor(s). Choice of the proper AB system 24 facilitated production of tetrahydrofuran 38. With the full skeleton in place, 38 was efficiently epoxidized and oxidized to 4. 12-Noralliacolide (4) served as an appropriate relay substrate for conversion to alliacol A (2) and several other alliacanes.

  DOI：

  10.1021/jo00120a027
• 作为产物：
  描述：

  3-[2-(2-[1,3]Dioxan-2-yl-ethyl)-[1,3]dithian-2-yl]-cyclopentanone 在 吡啶 、 盐酸 、 4-二甲氨基吡啶 、 ruthenium trichloride 、 氢氧化钾 、 sodium periodate 、 copper(l) iodide 、 lithium aluminium tetrahydride 、 高氯酸 、 草酰氯 、 2,6-二叔丁基-4-甲基苯酚 、 sodium methylate 、 trimethoxonium tetrafluoroborate 、 L-Selectride 、 二异丁基氢化铝 、 碳酸氢钠 、 sodium carbonate 、 potassium carbonate 、 对甲苯磺酸 、 二甲基亚砜 、 三乙胺 、 间氯过氧苯甲酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 四氯化碳 、 六甲基磷酰三胺 、 乙醚 、 正己烷 、 二氯甲烷 、 环己烷 、 甲苯 、 乙腈 、 苯 为溶剂， 反应 245.78h， 生成 (+/-)-12-Noralliacolide
  参考文献：
  名称：

  A Stereoselective Total Synthesis of (.+-.)-Alliacol A and Congeners of Marasmius Alliaceus

  摘要：

  Synthesis of alliacolide(1), alliacol A (2), and 12-noralliacolide (4), members of the alliacane family of sesquiterpene lactones, was accomplished through both syn- and anti-modes of intramolecular S-N' displacement. Two routes to 12-noralliacolide (4) are presented, which contrast brevity and efficiency in stereoselection (i.e. 14 --> 16/17 versus 37a/b --> 38). Since both routes culminate in C-ring annulation, introduction of the correct stereochemical arrangement relied heavily on the structural features of the hydrindane (AB) precursor(s). Choice of the proper AB system 24 facilitated production of tetrahydrofuran 38. With the full skeleton in place, 38 was efficiently epoxidized and oxidized to 4. 12-Noralliacolide (4) served as an appropriate relay substrate for conversion to alliacol A (2) and several other alliacanes.

  DOI：

  10.1021/jo00120a027

文献信息

• A stereoselective total synthesis of alliacane lactones
  作者：Peter T. Lansbury、James J. La Clair

  DOI：10.1016/0040-4039(93)88051-j

  日期：1993.7

  Sesquiterpene lactones of the alliancane type have been synthesized for the first time with complete stereocontrol during enolate addition to hydrindenones and intramolecular SN' cyclizations onto allylic chloroacetates.

  烯丙基类型的倍半萜内酯是首次合成的，在烯醇加成氢化茚烯酮和分子内SN'环化成烯丙基氯乙酸酯的过程中具有完全的立体控制。
• Total Synthesis of (±)-12-noralliacolide, (±)-alliacol A and (±)-alliacolide
  作者：Peter T. Lansbury、Ben-xin Zhi

  DOI：10.1016/s0040-4039(00)82176-0

  日期：1988.1
• LANSBURY, PETER T.;ZHI, BEN-XIN, TETRAHEDRON LETT., 29,(1988) N 45, C. 5735-5738
  作者：LANSBURY, PETER T.、ZHI, BEN-XIN

  DOI：——

  日期：——
• A Stereoselective Total Synthesis of (.+-.)-Alliacol A and Congeners of Marasmius Alliaceus
  作者：James J. La Clair、Peter T. Lansbury、Ben-xin Zhi、Karst Hoogsteen

  DOI：10.1021/jo00120a027

  日期：1995.7

  Synthesis of alliacolide(1), alliacol A (2), and 12-noralliacolide (4), members of the alliacane family of sesquiterpene lactones, was accomplished through both syn- and anti-modes of intramolecular S-N' displacement. Two routes to 12-noralliacolide (4) are presented, which contrast brevity and efficiency in stereoselection (i.e. 14 --> 16/17 versus 37a/b --> 38). Since both routes culminate in C-ring annulation, introduction of the correct stereochemical arrangement relied heavily on the structural features of the hydrindane (AB) precursor(s). Choice of the proper AB system 24 facilitated production of tetrahydrofuran 38. With the full skeleton in place, 38 was efficiently epoxidized and oxidized to 4. 12-Noralliacolide (4) served as an appropriate relay substrate for conversion to alliacol A (2) and several other alliacanes.