(+/-)-vinoxine | 93630-65-0

• 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: (+/-)-vinoxine
• 英文别名: 16-epivinoxine；methyl (1S,11S,12S,13E)-13-ethylidene-15-(2-hydroxyethyl)-10,15-diazatetracyclo[10.3.1.02,10.04,9]hexadeca-2,4,6,8-tetraene-11-carboxylate
• CAS: 93630-65-0
• 化学式: C₂₀H₂₄N₂O₃
• 分子量: 340.422
• InChiKey: XXUSUMBPMCGKSK-ODASUXAUSA-N

物化性质

• 沸点：
  526.7±50.0 °C(Predicted)
• 密度：
  1.30±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  54.7
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (+/-)-vinoxine 在 platinum(IV) oxide 氢气 作用下， 以 甲醇 为溶剂， 反应 48.0h， 以60%的产率得到(+/-)-19,20α-Dihydrovinoxine
  参考文献：
  名称：

  Studies on the synthesis of mavacurine-type indole alkaloids. First total synthesis of (±)-2,7-dihydropleiocarpamine

  摘要：

  Closure of the six-membered C ring of pentacyclic mavacurine-type alkaloids from suitably substituted tetracyclic substructures embodying rings ABDE of these alkaloids, either by electrophilic cyclization upon the indole 3-position or by intramolecular alkylation of the piperidine nitrogen, failed. In contrast, 6a-homopleiocarpamine (45) has been synthesized from dithioacetal 42 by an electrophilic cyclization involving the closure of the seven-membered C ring. The first total synthesis of the alkaloid 2,7-dihydropleiocarpamine (68) has been achieved by photocyclization of the tetracyclic chloroacetamide 54 as the key step. The required tetracyclic ABDE ring systems were prepared by a straightforward sequence consisting of nucleophilic addition of a 1-indoleacetatic ester enolate to the gamma position of a pyridinium salt, acid cyclization of the resulting 1,4-dihydropyridine, and final elaboration of the (E)-ethylidene substituent. An alternative synthesis of the tetracyclic alkaloid vinoxine (10a) is also reported.

  DOI：

  10.1021/jo00079a021
• 作为产物：
  描述：

  吲哚-1-乙酸 在 盐酸 、 sodium tetrahydroborate 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 苯 为溶剂， 反应 22.0h， 生成 (+/-)-vinoxine
  参考文献：
  名称：

  吲哚生物碱长春花碱的全合成和立体化学重分配

  摘要：

  据报道，吲哚生物碱长春新碱的第一个全合成和该生物碱中碳16处相对构型的重新分配。

  DOI：

  10.1016/0040-4039(84)80023-4

文献信息

• An alternative synthesis of the indole alkaloid vinoxine
  作者：M.-Lluïsa Bennasar、Ester Zulaica、Juan-Miguel Jiménez、Joan Bosch

  DOI：10.1016/s0040-4039(00)94619-7

  日期：1990.1

  An alternative synthesis of (±)-vinoxine, based on the nucleophilic addition of an ester α-anion to a 3-acetylpyridinium salt, acid-induced cyclization of the resultant 1,4-dihydropyridine, and stereoselective elaboration of the ()-ethylidene substituent, is reported.

  （±）-长春碱的另一种合成方法，是基于将酯α-阴离子亲核加成至3-乙酰基吡啶鎓盐，酸诱导的1,4-二氢吡啶环合反应以及（）-亚乙基的立体选择性修饰报告了取代基。
• Total synthesis of (±)-vinoxine: construction of the bridged pyrido[1,2-<i>a</i>]indole skeleton <i>via</i> Tf₂O-mediated Bischler–Napieralski reaction and stereoselective radical cyclization
  作者：Kosuke Okada、Hirofumi Ueda、Hidetoshi Tokuyama

  DOI：10.1039/d2ob00274d

  日期：——

  The total synthesis of (±)-vinoxine was achieved featuring the assembly of a multi-substituted tetrahydropyrido[1,2-a]indole skeleton through the Tf2O-mediated Bischler–Napieralski reaction. The characteristic diazabicyclo[3.3.1]nonane skeleton was stereoselectively constructed via radical cyclization based on the one stereochemistry of the C3 position. The established methodology provides new options

  (±)-vinoxine的全合成是通过Tf 2 O介导的Bischler-Napieralski反应组装多取代的四氢吡啶并[1,2- a ]吲哚骨架来实现的。基于C3位置的一种立体化学，通过自由基环化立体选择性地构建了特征性的二氮杂双环[3.3.1]壬烷骨架。已建立的方法为合成含有多取代吡啶并[1,2- a ]吲哚骨架的天然产物和药物提供了新的选择。
• Concise Total Synthesis of (+)-Pleiocarpamine and Convergent Total Syntheses of (+)-Voacalgine A and (+)-Bipleiophylline via an Aerobic Oxidative Coupling
  作者：Kosuke Okada、Ken-ichi Ojima、Hirofumi Ueda、Hidetoshi Tokuyama

  DOI：10.1021/jacs.3c05811

  日期：2023.8.2

  The stereocontrolled total synthesis of (+)-pleiocarpamine and the total syntheses of (+)-voacalgine A and (+)-bipleiophylline have been achieved. The scalable and concise 10-step synthesis of (+)-pleiocarpamine features construction of stereochemistry at the C16 position by radical cyclization and that of the highly strained cage-like structure via Pd-catalyzed intramolecular aromatic C–H functionalization

  实现了(+)-多香果胺的立体控制全合成以及(+)-voacalgine A和(+)-bipleiophylline的全合成。(+)-pleiocarpamine 的可扩展且简洁的 10 步合成特点是通过自由基环化在 C16 位上构建立体化学，并通过 Pd 催化的分子内芳香族 C-H 官能化构建高应变的笼状结构。通过改进FePc(CO 2 H) 8催化色氨酸衍生物的仿生有氧氧化偶联，建立了合成的(+)-多香果胺与焦儿茶酸的氧化偶联生成(+)-voacalgine A。 +)-双茶碱通过(+)-voacalgine A与(+)-多效果肉胺的第二次偶联或2当量(+)-多效果肉胺与焦儿茶酸的一锅偶联来完成。
• 3-Arylcarbonyl-1H-indoles useful as therapeutic agents
  申请人：STERLING WINTHROP INC.

  公开号：EP0444451A2

  公开（公告）日：1991-09-04

  2-R₂-R₄-substituted-3-R₃-CO-1-[(C-attached-N-heteryl)-(Alk)n]-1H-indoles useful as analgesic, anti-rheumatic, anti-inflammatory or anti-glaucoma agents.

  2-R₂-R₄-取代的-3-R₃-CO-1-[(C-连接的-N-庚基)-(烷基)n]-1H-吲哚，可用作镇痛剂、抗风湿剂、消炎剂或抗青光眼剂。
• General method for the synthesis of bridged indole alkaloids. Nucleophilic addition of indoleacetic ester enolates to N-alkylpyridinium salts
  作者：M. Lluisa Bennasar、Mercedes Alvarez、Rodolfo Lavilla、Ester Zulaica、Joan Bosch

  DOI：10.1021/jo00291a013

  日期：1990.2