(14S,18R,20E)-16,16-dimethyl-5,7,15,17-tetraoxa-12-aza-pentacyclo[10.8.2.0^2,10.0^4,8.0^14,18]docosa-1(20),2,4(8),9-tetraen-13-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯氮卓类
• 英文名称: (14S,18R,20E)-16,16-dimethyl-5,7,15,17-tetraoxa-12-aza-pentacyclo[10.8.2.0^2,10.0^4,8.0^14,18]docosa-1(20),2,4(8),9-tetraen-13-one
• 英文别名: (1E,14S,18R)-16,16-dimethyl-5,7,15,17-tetraoxa-12-azapentacyclo[10.8.2.02,10.04,8.014,18]docosa-1(20),2,4(8),9-tetraen-13-one
• 化学式: C₁₉H₂₁NO₅
• 分子量: 343.379
• InChiKey: BKBWLGFMTHYMDQ-SWGCWBKJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  25
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  57.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  6-溴-3,4-亚甲基二氧苯甲醛 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 palladium diacetate 、 sodium tetrahydroborate 、 4 A molecular sieve 、 1,3-双(二苯基膦)丙烷 、 2-fluoro-1-ethylpyridinium tetrafluoroborate 、 N,N-二异丙基乙胺 、 silver carbonate 作用下， 以 甲醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 4.0h， 生成 (14S,18R,20E)-16,16-dimethyl-5,7,15,17-tetraoxa-12-aza-pentacyclo[10.8.2.0^2,10.0^4,8.0^14,18]docosa-1(20),2,4(8),9-tetraen-13-one
  参考文献：
  名称：

  Asymmetric Total Synthesis of the 1-epi-Aglycon of the Cripowellins A and B

  摘要：

  [GRAPHICS]The unusual [5.3.2]-bicyclic structure of the insecticidal Amaryllidaceae alkaloids cripowellin A (1) and B (2) has been synthesized for the first time via a sequence of Sharpless dihydroxylation, ring-closing metathesis, and intramolecular Heck reaction. The asymmetric synthesis of the 1-epiaglycon 82 proceeds with virtually complete diastereo- and enantioselectivity (de, ee >= 98%) in 13 steps and an overall yield of 5.6%. In addition, three alternative approaches toward the aglycon 3 are also described focusing on (1) the alkylation of the 2-benzazepinedithianes 35 and 36 with the electrophile 11, (2) a radical cyclization of the precursor (R/S,S,S)-39, and (3) an intramolecular arylation reaction of the aryl ketone 47.

  DOI：

  10.1021/jo0518093

文献信息

• CROPWELLLINS AND SYNTHETIC DERIVATIVES THEREOF USED AS MEDICAMENTS
  申请人：Antonicek Horst-Peter

  公开号：US20090131406A1

  公开（公告）日：2009-05-21

  The present invention relates to cripowellins and synthetic derivatives thereof for treating diseases of man and also, in particular, to their use for preparing a medicament for treating cancer or other proliferative disorders in man and animal. Furthermore, the present invention relates to novel cripowellin derivatives and processes for their preparation.

  本发明涉及cripowellins及其合成衍生物，用于治疗人类疾病，尤其是用于制备治疗人和动物癌症或其他增殖性疾病的药物。此外，本发明涉及新型cripowellin衍生物及其制备方法。
• Asymmetric Total Synthesis of the 1-<i>e</i><i>pi</i>-Aglycon of the Cripowellins A and B
  作者：Dieter Enders、Achim Lenzen、Michael Backes、Carsten Janeck、Kelly Catlin、Marie-Isabelle Lannou、Jan Runsink、Gerhard Raabe

  DOI：10.1021/jo0518093

  日期：2005.12.1

  [GRAPHICS]The unusual [5.3.2]-bicyclic structure of the insecticidal Amaryllidaceae alkaloids cripowellin A (1) and B (2) has been synthesized for the first time via a sequence of Sharpless dihydroxylation, ring-closing metathesis, and intramolecular Heck reaction. The asymmetric synthesis of the 1-epiaglycon 82 proceeds with virtually complete diastereo- and enantioselectivity (de, ee >= 98%) in 13 steps and an overall yield of 5.6%. In addition, three alternative approaches toward the aglycon 3 are also described focusing on (1) the alkylation of the 2-benzazepinedithianes 35 and 36 with the electrophile 11, (2) a radical cyclization of the precursor (R/S,S,S)-39, and (3) an intramolecular arylation reaction of the aryl ketone 47.