(4R,6R)-5,5-dimethyl-6-phenylmethoxynona-1,8-dien-4-ol | 1068635-54-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (4R,6R)-5,5-dimethyl-6-phenylmethoxynona-1,8-dien-4-ol
• CAS: 1068635-54-0
• 化学式: C₁₈H₂₆O₂
• 分子量: 274.403
• InChiKey: NXUYOWVFMBWGQW-IAGOWNOFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  20
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 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：

  (4R,6R)-5,5-dimethyl-6-phenylmethoxynona-1,8-dien-4-ol 在 碘 、 碳酸氢钠 作用下， 以 水 、 乙醚 为溶剂， 反应 8.0h， 以87%的产率得到(2R,4R,6S)-6-(iodomethyl)-3,3-dimethyl-4-phenylmethoxy-2-prop-2-enyloxane
  参考文献：
  名称：

  Benzylpedamide 的正式全合成：(+)-Pederin 的右半部分

  摘要：

  (+)-pederin 的右半部分是通过方便有效的不对称合成 14 步合成的，总产率为 8.3%。关键步骤是碘诱导的杂环化以构建吡喃环。手性中心是通过不对称烯丙基化、底物控制的非对映选择性反应和 Sharpless 不对称二羟基化分别构建的。

  DOI：

  10.1055/s-2008-1077788
• 作为产物：
  描述：

  2,2-二甲基-1,3-丙二醇 在 bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 四丁基碘化铵 、 sodium hydride 、 caesium carbonate 、 4-氯-3-硝基苯甲酸 、 (S)-(-)-5,5-二氯-6,6-二甲氧基-2,2-双(二苯基磷酸)-1,1-联苯基 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 N,N-二甲基甲酰胺 为溶剂， 反应 75.0h， 生成 (4R,6R)-5,5-dimethyl-6-phenylmethoxynona-1,8-dien-4-ol
  参考文献：
  名称：

  Studies toward the Unique Pederin Family Member Psymberin: Full Structure Elucidation, Two Alternative Total Syntheses, and Analogs

  摘要：

  Two synthetic approaches to psymberin have been accomplished. A highly convergent first generation synthesis led to the complete stereochemical assignment and demonstrated that psymberin and irciniastatin A are identical compounds. This synthesis featured a diastereoselective aldol coupling between the aryl fragment and a central tetrahydropyran core and a novel one-pot procedure to convert an amide, via intermediacy of a sensitive methyl imidate, to the N-acyl aminal reminiscent of psymberin. The highlights of the second generation synthesis include an efficient iridium-catalyzed enantioselective bisallylation of neopentyl glycol and a stepwise Sonogashira coupling/cycloisomerization/reduction sequence to construct the dihydroisocoumarin unit. The two synthetic avenues were achieved in 17-18 steps (longest linear sequence, similar to 14-15 isolations) from 3 fragments prepared in 7-8 (first generation) and 3-8 (second generation) steps each. This convergent approach allowed for the preparation of sufficient amounts of psymberin (similar to 0.5 g) for follow-up biological studies. Meanwhile, our highly flexible strategy enabled the design and synthesis of multiple analogs, including a psymberin pederin hybrid, termed psympederin, that proved crucial to a comprehensive understanding of the chemical biology of psymberin and related compounds that will be described in a subsequent manuscript.

  DOI：

  10.1021/ja3057612

文献信息

• Studies toward the Unique Pederin Family Member Psymberin: Full Structure Elucidation, Two Alternative Total Syntheses, and Analogs
  作者：Yu Feng、Xin Jiang、Jef K. De Brabander

  DOI：10.1021/ja3057612

  日期：2012.10.17

  Two synthetic approaches to psymberin have been accomplished. A highly convergent first generation synthesis led to the complete stereochemical assignment and demonstrated that psymberin and irciniastatin A are identical compounds. This synthesis featured a diastereoselective aldol coupling between the aryl fragment and a central tetrahydropyran core and a novel one-pot procedure to convert an amide, via intermediacy of a sensitive methyl imidate, to the N-acyl aminal reminiscent of psymberin. The highlights of the second generation synthesis include an efficient iridium-catalyzed enantioselective bisallylation of neopentyl glycol and a stepwise Sonogashira coupling/cycloisomerization/reduction sequence to construct the dihydroisocoumarin unit. The two synthetic avenues were achieved in 17-18 steps (longest linear sequence, similar to 14-15 isolations) from 3 fragments prepared in 7-8 (first generation) and 3-8 (second generation) steps each. This convergent approach allowed for the preparation of sufficient amounts of psymberin (similar to 0.5 g) for follow-up biological studies. Meanwhile, our highly flexible strategy enabled the design and synthesis of multiple analogs, including a psymberin pederin hybrid, termed psympederin, that proved crucial to a comprehensive understanding of the chemical biology of psymberin and related compounds that will be described in a subsequent manuscript.
• Formal Total Synthesis of Benzylpedamide: The Right Half of (+)-Pederin
  作者：Ying Li、Degang Liu、Jijun Xue、Zhixiang Xie、Liping Wei、Xianshu Zhang

  DOI：10.1055/s-2008-1077788

  日期：2008.6

  The right half of (+)-pederin was synthesized through a convenient and efficient asymmetric synthesis in 14 steps with 8.3% overall yield. The key step was an iodine-induced heterocyclization to construct the pyran ring. The chiral centers were constructed separately via asymmetric allylation, substrate-controlled diastereoselective reactions, and Sharpless asymmetric dihydroxylation.

  (+)-pederin 的右半部分是通过方便有效的不对称合成 14 步合成的，总产率为 8.3%。关键步骤是碘诱导的杂环化以构建吡喃环。手性中心是通过不对称烯丙基化、底物控制的非对映选择性反应和 Sharpless 不对称二羟基化分别构建的。