(+)-12-[(2'R,5'S,6'R)-5'-hydroxy-6'-(hydroxymethyl)piperidin-2'-yl]dodecan-3-one | 14058-39-0

• 分子结构分类: 有机化合物 - 生物碱及其衍生物
• 英文名称: (+)-12-[(2'R,5'S,6'R)-5'-hydroxy-6'-(hydroxymethyl)piperidin-2'-yl]dodecan-3-one
• 英文别名: (+)-prosopinine；12-[(2R,5S,6R)-5-hydroxy-6-(hydroxymethyl)piperidin-2-yl]dodecan-3-one
• CAS: 14058-39-0
• 化学式: C₁₈H₃₅NO₃
• 分子量: 313.481
• InChiKey: KYBOBXNXZQTAKA-NXHRZFHOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  22
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  69.6
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  10-溴癸醛 在 copper(I) bromide dimethylsulfide complex 、 Celite 、 三氟化硼乙醚 、 四丁基氟化铵 、 lithium 、 对甲苯磺酸 、 pyridinium chlorochromate 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 9.0h， 生成 (+)-12-[(2'R,5'S,6'R)-5'-hydroxy-6'-(hydroxymethyl)piperidin-2'-yl]dodecan-3-one
  参考文献：
  名称：

  Rhodium-Catalyzed Cyclohydrocarbonylation:  Application to the Synthesis of (+)-Prosopinine and (−)-Deoxoprosophylline

  摘要：

  Efficient convergent total syntheses of (+)-prosopinine (1) and (-)-deoxoprosophylline (4) were accomplished using Rh-BIPHEPHOS complex-catalyzed cyclohydrocarbonylation as the key step. The Rh-BIPHEPHOS complex-catalyzed cyclohydrocarbonylation of I, derived from (R)-serine, at 65 degrees C and 4 atm of CO and H-2 (1:1) in ethanol afforded 6-ethoxypiperidine II, which was transformed to enantiopure (+)-prosopinine (1) in 3 steps. In a similar manner, (-)-deoxoprosophylline was synthesized through cyclohydrocarbonylation of IV derived from (S)-serine, giving 6-ethoxypiperidine V. The key intermediate V was transformed to enantiopure (-)-deoxoprosophylline (4) in 4 steps. These two short total syntheses clearly demonstrate the usefulness of the extremely regioselective cyclohydrocarbonylation process developed in these laboratories for the concise syntheses of piperidine alkaloids and related compounds.

  DOI：

  10.1021/jo9815608

文献信息

• 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。
• Transition Metal-Mediated Stereocontrolled Cyclization of Urethanes Leading to Versatile Fused Piperidines and Its Application to the Synthesis of (+)-Prosopinine and (+)-Palustrine
  作者：Yoshiro Hirai、Joshu Watanabe、Tetsuya Nozaki、Hajime Yokoyama、Seiji

  DOI：10.1021/jo961951r

  日期：1997.2.1
• Rhodium-Catalyzed Cyclohydrocarbonylation:  Application to the Synthesis of (+)-Prosopinine and (−)-Deoxoprosophylline
  作者：Iwao Ojima、Ephraim S. Vidal

  DOI：10.1021/jo9815608

  日期：1998.10.1

  Efficient convergent total syntheses of (+)-prosopinine (1) and (-)-deoxoprosophylline (4) were accomplished using Rh-BIPHEPHOS complex-catalyzed cyclohydrocarbonylation as the key step. The Rh-BIPHEPHOS complex-catalyzed cyclohydrocarbonylation of I, derived from (R)-serine, at 65 degrees C and 4 atm of CO and H-2 (1:1) in ethanol afforded 6-ethoxypiperidine II, which was transformed to enantiopure (+)-prosopinine (1) in 3 steps. In a similar manner, (-)-deoxoprosophylline was synthesized through cyclohydrocarbonylation of IV derived from (S)-serine, giving 6-ethoxypiperidine V. The key intermediate V was transformed to enantiopure (-)-deoxoprosophylline (4) in 4 steps. These two short total syntheses clearly demonstrate the usefulness of the extremely regioselective cyclohydrocarbonylation process developed in these laboratories for the concise syntheses of piperidine alkaloids and related compounds.