(S)-4-phenyl-1,5-diazacyclononan-2-one | 112020-25-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (S)-4-phenyl-1,5-diazacyclononan-2-one
• 英文别名: (4S)-4-phenyl-1,5-diazonan-2-one
• CAS: 112020-25-4
• 化学式: C₁₃H₁₈N₂O
• 分子量: 218.299
• InChiKey: KJAKZNQHLRZRQW-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  41.1
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-4-phenyl-1,5-diazacyclononan-2-one 在 镍 吡啶 、 sodium hydroxide 、 氢气 、 sodium ethanolate 作用下， 以 ammonium hydroxide 、 乙醇 、 二氯甲烷 、 甲苯 为溶剂， 25.0~55.0 ℃ 、344.73 kPa 条件下， 反应 331.0h， 生成 (2S)-9-acetyl-2-phenyl-1,5,9-triazacyclotridecan-4-one
  参考文献：
  名称：

  生物碱美福林和N（1）-乙酰基-N（1）-脱氧美福林的不对称合成

  摘要：

  描述了亚精胺生物碱（-）-美福林（11）和（+）- N（1）-乙酰基-N（1）-脱氧美福林（12）的总合成。这些大环内酰胺属于自然界中非常常见的多胺衍生物的最令人感兴趣的缀合物。对映选择性的合成是通过对其（+）-L-酒石酸盐进行重结晶而拆分3-氨基-3-苯基丙酸甲酯（2）而实现的。随后通过缩合，还原性环扩展（内部键断裂）以及最后一个涉及第二个环扩展的转酰胺基反应，来构建13元环。

  DOI：

  10.1002/hlca.19960790417
• 作为产物：
  描述：

  (S)-(-)-1,5-Diaza-4-phenylbicyclo<4.3.0>nonan-2-one 在 氨 、 sodium 作用下， 以94%的产率得到(S)-4-phenyl-1,5-diazacyclononan-2-one
  参考文献：
  名称：

  Chiral Vinyl Sulfoxides as Useful Reagents for the Synthesis of β-Amino Acid Derivatives

  摘要：

  DOI：

  10.1080/10426509708545604

文献信息

• Conjugate addition of 6-membered hydrazine to chiral tert-butyl (E)-2-(p-tolylsulfinyl)cinnamates. Synthesis of (S)-celacinnine
  作者：Haruo Matsuyama、Nobuhiro Itoh、Aoi Matsumoto、Nahoko Ohira、Kenji Hara、Masato Yoshida、Masahiko Iyoda

  DOI：10.1039/b107443c

  日期：2001.11.15

  Two enantiomers of the bicyclic lactam, (S)- and (R)-9-phenyl-1,6-diazabicyclo[4.3.0]nonan-7-one (6), were synthesized stereoselectively with high optical purity (95% ee) by the asymmetric conjugate addition–cyclization of piperidazine to chiral vinyl sulfoxides, tert-butyl (E)-2-[(R)- and (S)-p-tolylsulfinyl]cinnamate (4), followed by removal of the p-tolylsulfinyl group with SmI2. The subsequent reductive cleavage of the N–N bond of the bicyclic lactam 6 with sodium in liquid ammonia produced the corresponding 9-membered azalactam, (S)- and (R)-4-phenyl-1,5-diazacyclononan-2-one (7) with 99% and 97% ee, respectively. X-Ray crystallography showed that (S)-7 exists exclusively as a trans conformer in the crystal state. Starting from (S)-7, naturally occurring (S)-celacinnine 1 was synthesized with 99% ee employing the ring-expansion reaction via intramolecular transamidation.

  双环内酰胺的两个对映体，(S)-和(R)-9-苯基-1,6-二氮杂双环[4.3.0]壬烷-7-酮（6），通过手性乙烯基亚砜与哌啶嗪的不对称共轭加成-环化反应，后进行SmI2去对甲苯亚砜基，以高光学纯度（95% ee）进行立体选择性合成。随后，通过在液氨中使用钠对双环内酰胺6的N–N键进行还原裂解，分别得到相应的9元氮内酰胺，(S)-和(R)-4-苯基-1,5-二氮杂环壬烷-2-酮（7），其光学纯度分别为99%和97% ee。X射线晶体学显示，(S)-7在晶态下仅以trans构象存在。以(S)-7为起始物，通过环扩张反应经分子内转氨反应合成了天然存在的(S)-celacinnine 1，其光学纯度为99% ee。
• Diastereoselective Conjugate Addition of Cyclic Hydrazine to Optically Active Vinyl Sulfoxide. A Novel Synthesis of Optically Active Azalactams
  作者：Haruo Matsuyama、Nobuhiro Itoh、Nobumasa Kamigata

  DOI：10.1246/cl.1990.1547

  日期：1990.9

  Optically active (R)-(+)-l,5-diaza-4-phenylbicyclo[4.3.0]nonan-2-one (5) was prepared in high optical purity by diastereoselective conjugate addition of piperidazine to optically active (E)-(S)-1-(...

  通过哌嗪与旋光 (E) 的非对映选择性共轭加成以高光学纯度制备旋光 (R)-(+)-1,5-二氮杂-4-苯基双环 [4.3.0] 壬烷-2-酮 (5) -(S)-1-(...
• Itoh, Nobuhiro; Matsuyama, Haruo; Yoshida, Masato, Heterocycles, 1995, vol. 41, # 3, p. 415 - 418
  作者：Itoh, Nobuhiro、Matsuyama, Haruo、Yoshida, Masato、Kamigata, Nobumasa、Iyoda, Masahiko

  DOI：——

  日期：——
• Studies on the Synthesis of Optically Active Azalactams
  作者：Haruo Matsuyama、Michio Kobayashi、Harry H. Wasserman

  DOI：10.3987/r-1987-01-0085

  日期：——
• Chiroptical Properties of the Protoverbine Class of Macrocyclic Spermine Alkaloids
  作者：Konstantin Drandarov、Armin Guggisberg、Anthony Linden、Manfred Hesse

  DOI：10.1002/(sici)1522-2675(19981007)81:10<1773::aid-hlca1773>3.0.co;2-x

  日期：1998.10.7

  The chiroptical properties (circular dichroism, CD) of the 17-membered macrocyclic spermine lactam alkaloids (-)-protoverbine (16), its N,N'-methylene-bridged natural analogue (+)-protomethine (17), their natural derivatives (-)-verbacine (1), (-)-verballocine (2), (-)-verbascenine (3), (-)-verballoscenine (4), (+) verbamethine (5), (+)-incasine C (6), (+)-verdoline (incasine B', 30), (+)-incasine B (31), and some of their isosteric analogues were studied. By chemical and chiroptical correlation, it was confirmed that an amidically bonded (S)-beta-phenyl-beta-alanine fragment forms the chiral moiety in all of these natural compounds The signs of the registered Cotton effects (CEs) are interpreted in terms of the Smith's quadrant rule for the L-1(b) CEs of chiral a-substituted benzylamines and the Ogura's sign rule for n --> pi* CEs of lactams. Some of the conclusions regarding configuration are supported for the rigid bicyclic compound (-)-(9S)-9-phenyl-1,6-diazabicyclo[4.3.1]decan-7-one (15) by the X-ray crystal structure of the racemate.