(+/-)-20-epi-pseudovincadifformine | 73837-57-7

• 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: (+/-)-20-epi-pseudovincadifformine
• 英文别名: Pseudovincadifformine；(+/-)-Pseudovincadifformine；methyl (1S,12R,14R,19R)-14-ethyl-8,16-diazapentacyclo[10.6.1.01,9.02,7.016,19]nonadeca-2,4,6,9-tetraene-10-carboxylate
• CAS: 73837-57-7
• 化学式: C₂₁H₂₆N₂O₂
• 分子量: 338.45
• InChiKey: HVESDSXDWBFBHK-AJQWGZMRSA-N

物化性质

• 沸点：
  480.7±45.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  41.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (+/-)-20-epi-pseudovincadifformine 在 次氯酸叔丁酯 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 生成
  参考文献：
  名称：

  Syntheses of 20'-deoxyvinblastine, 20'-deoxyleurosidine, 20'-deoxyvincovaline, 20'-epi-20'-deoxyvincovaline, and 20'-deoxyvincristine and its 20'-epimer through racemic and enantioselectively generated intermediates. New syntheses of D/E-cis- and trans-.PSI.-vincadifformines and D/E-cis- and -trans-20-epi-.PSI.-vincadifformines

  摘要：

  DOI：

  10.1021/jo00275a029
• 作为产物：
  描述：

  Benzoic acid 3-[2-(3-ethyl-piperidin-1-yl)-ethyl]-1H-indol-2-ylmethyl ester 在 吡啶 、 盐酸 、 sodium tetrahydroborate 、 水 、 乙酸酐 、 sodium hydride 、 间氯过氧苯甲酸 作用下， 以 甲醇 、 二氯甲烷 、 二甲基亚砜 、 苯 为溶剂， 反应 28.83h， 生成 (+/-)-20-epi-pseudovincadifformine
  参考文献：
  名称：

  Kalaus, Gyoergy; Kiss, Miklos; Kajtar-Peredy, Maria, Heterocycles, 1985, vol. 23, # 11, p. 2783 - 2788

  摘要：

  DOI：

文献信息

• Recycling Upstream Redox Enzymes Expands the Regioselectivity of Cycloaddition in Pseudo-Aspidosperma Alkaloid Biosynthesis
  作者：Mohamed O. Kamileen、Matthew D. DeMars、Benke Hong、Yoko Nakamura、Christian Paetz、Benjamin R. Lichman、Prashant D. Sonawane、Lorenzo Caputi、Sarah E. O’Connor

  DOI：10.1021/jacs.2c08107

  日期：2022.11.2

  allows cycloaddition reactions with alternative regioselectivity. By incubating dehydrosecodine with reductase and oxidase biosynthetic enzymes that act upstream in the pathway, we can access the rare pseudoaspidosperma alkaloids pseudo-tabersonine and pseudo-vincadifformine, both in vitro and by reconstitution in the plant Nicotiana benthamiana from an upstream intermediate. We propose a stepwise mechanism

  大自然使用环加成反应来生成复杂的天然产物支架。Dehydrosecodine 是一种高反应性生物合成中间体，它经过环加成反应生成几种生物碱骨架，这些骨架是长春花碱和伊博加因等具有重要药理学意义的化合物的前体。在这里，我们报告了脱氢仲可定如何进行氧化还原化学反应，这反过来又允许进行具有替代区域选择性的环加成反应。通过将脱氢秒可定与作用于该通路上游的还原酶和氧化酶生物合成酶一起孵育，我们可以在体外和通过在植物本塞姆氏烟草中重组获得稀有的拟刺孢植物生物碱伪塔贝松碱和伪长春二福明来自上游中间体。我们提出了一种逐步机制，通过对酶中间体进行结构表征和监测氘标记的掺入来解释伪塔贝松碱支架的形成。这一发现突出了植物如何使用氧化还原酶从常见前体对映选择性地生成新支架。
• Studies in biomimetic alkaloid syntheses. 5. Studies syntheses of .psi.-vincadifformine, 20-epi-.psi.-vincadifformine, pandoline, 20-epipandoline, and the C-16 epimeric(carbomethoxy)velbanamines
  作者：Martin E. Kuehne、Curtis L. Kirkemo、Thomas H. Matsko、John C. Bohnert

  DOI：10.1021/jo01304a023

  日期：1980.8
• Total Syntheses of Vincadifformine, 3-Oxovincadifformine, Pseudo- and 20-<i>epi</i>-Pseudovincadifformine, Tabersonine, and Δ¹⁸-Tabersonine through Radical Reactions and Heck Reactions
  作者：Martin E. Kuehne、Tiansheng Wang、Pamela J. Seaton

  DOI：10.1021/jo960607r

  日期：1996.1.1

  The pentacyclic alkaloids vincadifformine (9), psi-vincadifformine (15), and epi-psi-vincadifformine (16) could be synthesized by intramolecular free-radical-induced cyclizations of the tetracyclic intermediates 7, 8, and 18, which were respectively obtained by condensation of the indoloazepine 1 with 2-(phenylselenyl)butyraldehyde and subsequent N-b-alkylation of the resulting tetracyclic amines 2 and 3, or from condensation of (phenylselenyl)acetaldehyde with the alkylated indoloazepine 17. The intermediates 2 and 3 also gave 3-oxovincadifformine (21) by an intermolecular radical alkylation with methyl acrylate. Their alkylation with (Z)-1,3-diiodopropene, phenyl selenoxide elimination, and intramolecular Heck reactions provided tabersonine (24) and 18,19-didehydrotabersonine (27).
• A common intermediate providing syntheses of .PSI.-tabersonine, coronaridine, iboxyphylline, ibophyllidine, vinamidine, and vinblastine
  作者：William G. Bornmann、Martin E. Kuehne

  DOI：10.1021/jo00032a029

  日期：1992.3

  Generation of the key tetracyclic intermediates 14a,b in six steps (42% overall) and subsequent short reduction, oxidation, and arylation sequences results in total syntheses of the title compounds 8, 9, 10, 11, 12, and 13.
• Synthesis of vinca alkaloids and related compounds. 64. Total syntheses of (.+-.)-pseudovincadifformine and (.+-.)-20-epipseudovincadifformine
  作者：Gyorgy Kalaus、Istvan Greiner、Maria Kajtar-Peredy、Janos Brlik、Lajos Szabo、Csaba Szantay

  DOI：10.1021/jo00074a039

  日期：1993.10

  Using our previously reported convergent synthetic strategy, secondary amine 6 and aldehyde 9 reacted to give tetracyclic esters 10 and 11, which readily led to pentacyclic lactams 14-16. Selective reduction of these products gave (+/-)-pseudovincadifformine (4), (+/-)-20-epipseudovincadifformine (5), and (+/-)-14-epipseudovincadifformine (20). Aldehyde 23 was also prepared and could be directly used for synthesizing (+/-)-20-epipseudovincadifformine (5). The introduction of the double bond into ring D of the pseudoaspidospermane skeleton was successfully achieved to obtain 21-oxopseudotabersonine (30).