(+/-)-1-benzyl-2-oxopiperidine-5-carbaldehyde | 132565-55-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: (+/-)-1-benzyl-2-oxopiperidine-5-carbaldehyde
• 英文别名: N-Benzyl-5-formyl-2-piperidone；1-Benzyl-6-oxopiperidine-3-carbaldehyde；1-benzyl-6-oxopiperidine-3-carbaldehyde
• CAS: 132565-55-0
• 化学式: C₁₃H₁₅NO₂
• 分子量: 217.268
• InChiKey: YFDJIFPORPZVSY-UHFFFAOYSA-N

物化性质

• 沸点：
  410.0±45.0 °C(Predicted)
• 密度：
  1.214±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  37.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  甲基三苯基溴化膦 、 (+/-)-1-benzyl-2-oxopiperidine-5-carbaldehyde 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 1.33h， 以64mg的产率得到1-benzyl-5-vinylpiperidin-2-one
  参考文献：
  名称：

  Bredt规则捕获的Kulinkovich-de Meijere反应的碳环氨基酮

  摘要：

  Ti II介导的由烯烃和酰胺形成的环丙胺，Kulinkovich-de Meijere反应涉及两个碳-碳键形成步骤。如果第二步需要形成桥头双键，则三环中间体的战略性使用可中止该过程。使用此Bredt规则约束会产生碳环氨基酮（关键生物碱构件）的产生。

  DOI：

  10.1002/anie.201509983
• 作为产物：
  描述：

  5-(羟基甲基)-1-(苯基甲基)-2-哌啶酮 在 三氧化硫吡啶 、 二甲基亚砜 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 (+/-)-1-benzyl-2-oxopiperidine-5-carbaldehyde
  参考文献：
  名称：

  Bredt规则捕获的Kulinkovich-de Meijere反应的碳环氨基酮

  摘要：

  Ti II介导的由烯烃和酰胺形成的环丙胺，Kulinkovich-de Meijere反应涉及两个碳-碳键形成步骤。如果第二步需要形成桥头双键，则三环中间体的战略性使用可中止该过程。使用此Bredt规则约束会产生碳环氨基酮（关键生物碱构件）的产生。

  DOI：

  10.1002/anie.201509983

文献信息

• Synthesis of (+)-Kuraramine
  作者：Timothy Gallagher、Fabio Frigerio、Claire Haseler

  DOI：10.1055/s-0029-1219377

  日期：2010.3

  The first synthesis of (+)-kuraramine via oxidative cleavage of (-)-N-methylcytisine is reported. An alternative but unsuccessful approach to (+)-kuraramine is also described based on extending an intramolecular enolate addition protocol that had previously been applied successfully to cytisine.

  报告首次报道了通过氧化裂解(-)-N-甲基胞嘧啶合成(+)-仓胺。报告还介绍了另一种合成(+)-呋喃丙胺的方法，但未获成功，这种方法是基于扩展分子内烯醇加成协议，该协议此前曾成功应用于胞嘧啶的合成。
• New synthesis of nitrogen heterocycles through amide-directed hydrocarbonylation of alkenamides catalyzed by rhodium complexes
  作者：Iwao Ojima、Anna Korda、William R. Shay

  DOI：10.1021/jo00006a013

  日期：1991.3

  Amide-directed hydrocarbonylation of 3-butenamide (1) catalyzed by rhodium complexes such as RhCl(PPh3)3, RhCl(CO)(PPh3)2, HRh(CO)(PPh3)3, and Rh4(CO)12 gives a mixture of 3,4-dihydro-2-pyridone (2), 4-methyl-3-pyrrolin-2-one (3), and a unique heterodimer, 6-(4-methyl-2-oxo-3-pyrrolin-1-yl)-2-piperidone (4). Dihydropyridone (2) is obtained in 88% yield with 98% selectivity by using HRh(CO)(PPh)3-dppb (2 equiv) catalyst system while 4 is yielded in 90% yield with 94% selectivity with the use of RhCl(PPh3)3-P(OPh)3 (10 equiv) as the catalyst. Control experiments revealed that this crossed coupling only proceeds in the copresence of rhodium catalyst, carbon monoxide, and hydrogen. The reactions of N-benzyl-3-butenamide (1a) gives a mixture of 1-benzyldihydropyridone (2a), 1-benzyl-4-methylpyrrolinone (3a), and 1-benzyl-6-formyl-3,4-dihydropyridone (5) and its 5-formyl isomer (6). The formation of 5 and 6 is suppressed by the addition of PPh3, and 2a is selectively isolated (72%) in the reaction using RhCl(CO)(PPh3)2-PPh3 (20 equiv) as the catalyst. The hydroformylation of 2a catalyzed by RhCl(PPh3)3 gives 5 in 80% isolated yield. The reaction of N-tert-butyl-3-butenamide (1b) gives a nearly 1:1 mixture of 1-tert-butyl-4-methylpyrrolinone (3b) and uncyclized N-tert-butyl-4-formylbutanamide (7) accompanied by a small amount of 1-tert-butyldihydropyridone (2b). In the reaction of N-trityl-3-butenamide (1c), no dihydropyridone (2c) was formed, and a mixture of 1-trityl-4-methylpyrrolinone (3c) (major) and N-trityl-4-formylbutanamide (8) (minor) is yielded. The reaction of 4-pentenamide gives 4-methyl-3,4-dihydro-2-pyridone (9) exclusively regardless of the structure of the rhodium catalysts used. Possible mechanisms for these reactions are discussed.
• Carbocyclic Amino Ketones by Bredt's Rule‐Arrested Kulinkovich–de Meijere Reaction
  作者：Paul B. Finn、Brenden P. Derstine、Scott McN. Sieburth

  DOI：10.1002/anie.201509983

  日期：2016.2.12

  reaction, involves two carbon–carbon bond‐forming steps. Strategic use of a tricyclic intermediate can arrest the process if the second step requires formation of a bridgehead double bond. Use of this Bredt's rule constraint results in the production of carbocyclic amino ketones, key alkaloid building blocks.

  Ti II介导的由烯烃和酰胺形成的环丙胺，Kulinkovich-de Meijere反应涉及两个碳-碳键形成步骤。如果第二步需要形成桥头双键，则三环中间体的战略性使用可中止该过程。使用此Bredt规则约束会产生碳环氨基酮（关键生物碱构件）的产生。