(+)-(S)-dodec-11-en-2-ol

• 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: (+)-(S)-dodec-11-en-2-ol
• 英文别名: (S)-dodec-11-en-2-ol；(2S)-dodec-11-en-2-ol
• 化学式: C₁₂H₂₄O
• 分子量: 184.322
• InChiKey: IHOLJZJZVIFXKA-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  13
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+)-(S)-dodec-11-en-2-ol 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 2,4,6-三氯苯甲酰氯 、 palladium 10% on activated carbon 、 氢气 、 三氯化硼 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 51.5h， 生成 (+)-aspicilin
  参考文献：
  名称：

  （+）‐ Aspicilin的不对称合成

  摘要：

  以（3 R，4 R）-1,5-己二烯-3,4-二醇和（S）-环氧丙烷为起始原料合成了具有四个立体中心的十八元大环内酯类阿斯匹西林（1）。在被保护的二烯二醇上进行的急剧的环氧化反应产生了所需的三个连续的立体中心，丙二酸酯的合成增加了乙酰基单元。应用Yamaguchi方案形成带有两个末端烯烃的关键酯，以准备进行开环复分解。经RCM，氢化，硒化，氧化和脱保护得到的阿斯匹西林总产率为4.7％。

  DOI：

  10.1002/jccs.201100587
• 作为产物：
  描述：

  10-十一烯-1-醇 在 乙酸乙烯酯 、 pyridinium chlorochromate 作用下， 以 乙醚 、 二氯甲烷 、 异丙醚 为溶剂， 反应 54.0h， 生成 (+)-(S)-dodec-11-en-2-ol
  参考文献：
  名称：

  Expedient Synthesis of (R)-Patulolide A

  摘要：

  An efficient derivation of the title compound has been formulated from easily accessible 10-undecenoic acid(1). Thus, dodec-11-en-2-ol (3), prepared from 1, was pyranylated and subjected to bromination with NBS followed by acetolysis to furnish (2E)-1-acetoxy-11-(tetrahydropyranyloxy)-dodec-2-ene (5). Its hydrolysis, oxidation, and depyranylation afforded the (2E)-hydroxy ester (9). This, on Candida rugosa lipase-catalyzed acetylation, SeO2 oxidation, hydrolysis, and Yamaguchi macrolactonization, led to (R)-patulolide A (I) with 67.1% ee. The enantiomeric excess was improved to 97% by first resolving the alcohol 3 via porcine pancreatic lipase catalyzed acetylation and converting the corresponding (R)-acetate (13) to I as done above.

  DOI：

  10.1021/jo951339k

文献信息

• Total Synthesis of (+)-Aspicilin from d-Mannitol
  作者：J. Yadav、T. Rao、K. Ravindar、B. Reddy

  DOI：10.1055/s-0029-1217974

  日期：2009.10

  The total synthesis of the 18-membered lichen macrolide, (+)-aspicilin, has been accomplished utilizing the Swem oxidation, Masamune-Roush olefination, and ring-closing metathesis of a trienic ester as key steps. D-Mannitol has been utilized as the chiral pool material for the construction of the olefinic aldehyde and the Jacobsen hydrolytic kinetic resolution has been employed for the construction

  18 元地衣大环内酯 (+)-aspicilin 的全合成已利用 Swem 氧化、Masamune-Roush 烯化和三烯酯的闭环复分解作为关键步骤完成。D-甘露醇已被用作构建烯醛的手性池材料，而雅各布森水解动力学拆分已被用于构建烯属膦酸酯。
• A Configurational Switch Based on Iridium-Catalyzed Allylic Cyclization: Application in Asymmetric Total Syntheses of Prosopis, Dendrobate, and Spruce Alkaloids
  作者：Christian Gnamm、Kerstin Brödner、Caroline M. Krauter、Günter Helmchen

  DOI：10.1002/chem.200901316

  日期：2009.10.12

  A method for the stereoselective synthesis of 2,6‐disubstituted piperidines has been developed that is based on the use of an intramolecular iridium‐catalyzed allylic substitution as a configurational switch. The procedure allows the preparation of 2‐vinylpiperidines with enantiomeric excesses (ee) of greater than 99 %. As applications, total syntheses of piperidine alkaloids have been elaborated,

  基于分子内铱催化的烯丙基取代作为构型转换，已开发出一种立体选择合成2,6-二取代哌啶的方法。该程序可以制备对映体过量（ee）大于99％的2-乙烯基哌啶。作为应用，已经详细说明了哌啶生物碱的总合成，大多数情况下是通过使用Ru催化的交叉金属作为引入侧链的关键步骤。描述了Prosopis生物碱（+）-prosopinine，（+）-prosophylline，（+）-prosopine和树状生物碱（+）-241D及其C6差向异构体的不对称总合成。
• Studies on PPL Catalyzed Acetylation of 2-Alkanols: Its Application for the Synthesis of 2-Dodecanol and 2-Tridecyl Acetate, the Pheromones of<i>Crematogaster</i>Ants and<i>Drosophila mulleri</i>Flies
  作者：Anubha Sharma、Archana S. Pawar、Subrata Chattopadhyay

  DOI：10.1080/00397919608003858

  日期：1996.1

  Several aliphatic 2-alkanols with varying chain length has been efficiently resolved by their acetylation using vinyl acetate/PPL in diisopropyl ether. The effect of solvent polarity, position and type of unsaturation and chain length has been probed. This has led to more convenient synthesis of some insect pheromones.
• Expedient Synthesis of (<i>R</i>)-Patulolide A
  作者：A. Sharma、S. Sankaranarayanan、S. Chattopadhyay

  DOI：10.1021/jo951339k

  日期：1996.1.1

  An efficient derivation of the title compound has been formulated from easily accessible 10-undecenoic acid(1). Thus, dodec-11-en-2-ol (3), prepared from 1, was pyranylated and subjected to bromination with NBS followed by acetolysis to furnish (2E)-1-acetoxy-11-(tetrahydropyranyloxy)-dodec-2-ene (5). Its hydrolysis, oxidation, and depyranylation afforded the (2E)-hydroxy ester (9). This, on Candida rugosa lipase-catalyzed acetylation, SeO2 oxidation, hydrolysis, and Yamaguchi macrolactonization, led to (R)-patulolide A (I) with 67.1% ee. The enantiomeric excess was improved to 97% by first resolving the alcohol 3 via porcine pancreatic lipase catalyzed acetylation and converting the corresponding (R)-acetate (13) to I as done above.
• Asymmetric Synthesis of (+)-Aspicilin
  作者：Chun-Yi Wang、Duen-Ren Hou

  DOI：10.1002/jccs.201100587

  日期：2012.3

  4‐diol and (S)‐propylene oxide as the starting materials. Sharpless epoxidation on the protected dienediol generated the required three consecutive stereocenters, and malonic ester synthesis added the acetyl unit. Yamaguchi protocol was applied to form the key ester with two terminal olefins ready for the ring‐closing metathesis. RCM, hydrogenation, selenylation, oxidation and deprotections gave aspicilin

  以（3 R，4 R）-1,5-己二烯-3,4-二醇和（S）-环氧丙烷为起始原料合成了具有四个立体中心的十八元大环内酯类阿斯匹西林（1）。在被保护的二烯二醇上进行的急剧的环氧化反应产生了所需的三个连续的立体中心，丙二酸酯的合成增加了乙酰基单元。应用Yamaguchi方案形成带有两个末端烯烃的关键酯，以准备进行开环复分解。经RCM，氢化，硒化，氧化和脱保护得到的阿斯匹西林总产率为4.7％。