(-)-16-chloro-1-dehydro-5-methoxy-vincadifformine | 159898-45-0

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 鸡蛋花型生物碱
• 英文名称: (-)-16-chloro-1-dehydro-5-methoxy-vincadifformine
• 英文别名: methyl (1R,10R,12S,17S,19S)-10-chloro-12-ethyl-17-methoxy-8,16-diazapentacyclo[10.6.1.01,9.02,7.016,19]nonadeca-2,4,6,8-tetraene-10-carboxylate
• CAS: 159898-45-0
• 化学式: C₂₂H₂₇ClN₂O₃
• 分子量: 402.921
• InChiKey: HRQZLEHTMVHBRY-XXBFSGCESA-N

物化性质

• 沸点：
  494.029±45.00 °C(Press: 760.00 Torr)(predicted)
• 密度：
  1.377±0.14 g/cm3(Temp: 25 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  51.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (-)-16-chloro-1-dehydro-5-methoxy-vincadifformine 以 甲醇 、 二氯甲烷 为溶剂， 反应 0.41h， 生成 (Z)-2-((3aS,5R,10bR,12bS)-5-Chloro-3a-ethyl-5-methoxycarbonyl-2,3,3a,4,5,12b-hexahydro-1H-6,12a-diaza-indeno[7,1-cd]fluoren-11-yl)-but-2-enedioic acid dimethyl ester
  参考文献：
  名称：

  Unexpected ring C enlargement of the aspidospermane skeleton

  摘要：

  Treatment of (-)-16-chloro-1-dehydro-5-methoxy-vineadifformine 4 with Ac2O-pyridine led to the rearranged compound 6 through an unexpected ring C expansion. Upon reaction with dimethyl acetylenedicarboxylate. 4 provided the [2+2] cycloaddition derivative 9 but did not undergo the ring C enlargement. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)01967-0
• 作为产物：
  描述：

  甲醇 、 16-chloro-1-dehydrovincadifformine-N4-oxyde 在 三氟乙酸酐 作用下， 生成 (-)-16-chloro-1-dehydro-5-methoxy-vincadifformine
  参考文献：
  名称：

  沙特色胺（-）长春花新碱

  摘要：

  从16-氯-1-脱氢vinadifformine-N4-氧化物2开始，分两步进行（1. Polonovski-Potier反应； 2。添加溴化氰），方法是在C-6上进行立体定向溴化，得到氰基差向异构体在C上的混合物。 -5，5和6。进一步还原该混合物提供了（-）6S-溴长春花碱8。

  DOI：

  10.1016/0040-4039(94)88269-x

文献信息

• New Rearrangement of an Aspidosperma Alkaloid. The First Biomimetic Entry in the Goniomitine Skeleton
  作者：Guy Lewin、Corinne Schaeffer、Pierre Herve Lambert

  DOI：10.1021/jo00116a009

  日期：1995.6

  The first biomimetic approach to the skeleton of goniomitine (12) from an Aspidosperma alkaloid is described. With 16-chloro-1-dehydro-5-methoxyvincadifforme (4) (easily available from vincadifformine (1) as starting material, the rearrangement is performed in two steps: (a) Oxidation of 4 by m-CPBA followed by methanolysis affords the hemiketal 10 with a tetrahydro-1,2-oxazine structure for ring C, and (b) acid-catalyzed reaction on 10 provides either a mixture of both rearranged compounds 15 and 16 or 15 alone according to reaction time. Mechanisms of formation of 10, 15, and 16 are discussed.
• Unexpected ring C enlargement of the aspidospermane skeleton
  作者：Guy Lewin、Corinne Schaeffer、Reynald Hocquemiller

  DOI：10.1016/s0040-4039(01)01967-0

  日期：2001.12

  Treatment of (-)-16-chloro-1-dehydro-5-methoxy-vineadifformine 4 with Ac2O-pyridine led to the rearranged compound 6 through an unexpected ring C expansion. Upon reaction with dimethyl acetylenedicarboxylate. 4 provided the [2+2] cycloaddition derivative 9 but did not undergo the ring C enlargement. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Nouvelle fonctionnalisation de la chaîne tryptamine de la (−) vincadifformine alcaloïde à squelette aspidospermane
  作者：Guy Lewin、Jacques Poisson

  DOI：10.1016/0040-4039(94)88269-x

  日期：1994.10

  Starting from 16-chloro-1-dehydrovincadifformine-N4-oxyde 2, a two-steps sequence (1. Polonovski-Potier reaction; 2. addition of cyanogen bromide) afforded through stereospecific bromination on C-6 the mixture of cyano epimers on C-5, 5 and 6. Further reduction of this mixture provided (−) 6S-bromovincadifformine 8.

  从16-氯-1-脱氢vinadifformine-N4-氧化物2开始，分两步进行（1. Polonovski-Potier反应； 2。添加溴化氰），方法是在C-6上进行立体定向溴化，得到氰基差向异构体在C上的混合物。 -5，5和6。进一步还原该混合物提供了（-）6S-溴长春花碱8。