(+)-goniomitine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂萘
• 英文名称: (+)-goniomitine
• 英文别名: 2-[(4aS,12aR)-4a-ethyl-2,3,4,5,6,12a-hexahydro-1H-indolo[1,2-a][1,8]naphthyridin-7-yl]ethanol
• 化学式: C₁₉H₂₆N₂O
• 分子量: 298.428
• InChiKey: CGWKMDYVWRDDRF-MOPGFXCFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  37.2
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  聚合甲醛 、 (+)-goniomitine 在 sodium cyanoborohydride 作用下， 以 水 、 溶剂黄146 为溶剂， 反应 3.0h， 以43%的产率得到(20S,21R)-4-methyl-goniomitine
  参考文献：
  名称：

  Semisynthesis of (+)- and (−)-goniomitine from (−)- and (+)-vincadifformine

  摘要：

  The first biomimetic semisynthesis of goniomitine has been accomplished in nine steps with 11% overall yield starting from vincadifformine. Natural (-)- and unnatural (+)-goniomitine were prepared from (+)- and (-)-vincadifformine, respectively. The evaluation of the antiproliferative effect of both enantiomers proved unnatural (+)-goniomitine to be more potent, but this enantiomer as well as some close derivatives displayed a moderate activity only. (c) 2012 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tet.2012.11.084
• 作为产物：
  描述：

  tert-butyl N-2-(6-benzyloxy-1-tert-butyldiphenylsilyloxyhexa-3,4-dien-3-yl)phenylcarbamate 在 Hoveyda-Grubbs catalyst second generation 、 5% Pd(II)/C(eggshell) 、 四丁基氟化铵 、 氢气 、 palladium(II) hydroxide 、 sodium hydride 、 potassium carbonate 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 丙醇 、 5,5-dimethyl-1,3-cyclohexadiene 、 乙醚 、 乙醇 、 乙酸乙酯 、 oil 为溶剂， 140.0 ℃ 、101.33 kPa 条件下， 反应 60.5h， 生成 (+)-goniomitine
  参考文献：
  名称：

  Total Syntheses of (−)- and (+)-Goniomitine

  摘要：

  The Stille coupling reaction of 3-(benzyloxymethyl)-1-(tert-butyldiphenylsiloxy)ethyl-1-(tributylstannyl)allene with N-(tert-butoxycarbonyl)-2-iodoaniline directly produced the corresponding 2-vinylindole derivative, which was Independently transformed into natural (-)-goniomitine and unnatural (+)-goniomitine via the cross-metathesis with chiral oxazolopiperidone lactams. The antiproliferative activity of the synthesized natural (-)-goniomitine in Mock and MDCK/MDR1 cells showed them to be more potent to retard cell growth than unnatural (+)-goniomitine.

  DOI：

  10.1021/ol200320z

文献信息

• Total Syntheses of <i>rac</i> ‐ and (+)‐Goniomitine
  作者：Eunjoon Park、Cheol‐Hong Cheon

  DOI：10.1002/adsc.201900801

  日期：2019.11.5

  Concise total syntheses of rac‐ and (+)‐goniomitine were developed. The cyanide‐catalyzed imino‐Stetter reaction of an aldimine, derived from ethyl 2‐aminocinnamate and either rac‐ or (S)‐α,β‐unsaturated aldehyde bearing a δ‐valerolactam at the β‐position, provided rac‐ or (S)‐indole‐3‐acetate carrying an α‐vinyl‐δ‐valerolactam scaffold at the 2‐position, respectively. Subsequent saturation of the

  开发了rac-和（+）-goniomitine的简明全合成方法。由2-氨基肉桂酸乙酯与rac-或（S）-α，β-不饱和醛在β位置带有δ-戊内酰胺的醛亚胺的氰化物催化的亚氨基-Stetter反应提供了rac或（S）带有α-乙烯基δ的吲哚-3-乙酸盐戊内酰胺支架分别位于2位。随后乙烯基饱和，然后用DIBAL-H处理，得到N-苄基保护的古尼米丁。仅需三步色谱柱分离，最终的脱苄基反应即可提供所需的天然产物。
• Structure of goniomitine, a new type of indole alkaloid
  作者：L Randriambola、J.-C Quirion、C Kan-Fan、H.-P Husson

  DOI：10.1016/s0040-4039(00)96059-3

  日期：1987.1

  The structure 1 proposed for goniomitine, an indole alkaloid isolated from the root bark of (Apocynoceae), was inferred from an analysis of its MS, 1H 13C NMR spectral data. A biogenetic scheme is proposed to account for the formation of from vincadifformine .

  从其（MS），1 H 13 C NMR光谱数据的分析中推断出了拟用于淋菌素的结构1，这是一种从（Apocynoceae）根皮中分离出来的吲哚生物碱。提出了一种生物遗传方案来解决长春藤碱的形成。
• Lithium Enolate with a Lithium‐Alkyne Interaction in the Enantioselective Construction of Quaternary Carbon Centers: Concise Synthesis of (+)‐Goniomitine
  作者：Yang Li、Elena Paola、Zongheng Wang、Gabriel Menard、Armen Zakarian

  DOI：10.1002/anie.202209987

  日期：2022.11.14

  We report a method for direct enantioselective alkylation of 3-alkynoic acids and 2,3-alkendioic acids that form quaternary stereogenic centers, and application of this method to the total enantioselective synthesis of complex alkaloid (+)-goniomitine. Crystallographic studies highlighted cation-π interactions between lithium and alkyne groups in the chiral lithium aggregate intermediate.

  我们报道了一种直接对映选择性烷基化形成四级立体中心的 3-炔酸和 2,3-链烯二酸的方法，并将该方法应用于复杂生物碱 (+)-goniomitine 的全对映选择性合成。晶体学研究强调了手性锂聚集中间体中锂和炔基之间的阳离子-π相互作用。
• RANDRIAMBOLA, L.;QUIRION, J. -C.;KAN-FAN, C.;HUSSON, H. -P., TETRAHEDRON LETT., 28,(1987) N 26, 2123-2126
  作者：RANDRIAMBOLA, L.、QUIRION, J. -C.、KAN-FAN, C.、HUSSON, H. -P.

  DOI：——

  日期：——
• Semisynthesis of (+)- and (−)-goniomitine from (−)- and (+)-vincadifformine
  作者：Guy Lewin、Guillaume Bernadat、Geneviève Aubert、Thierry Cresteil

  DOI：10.1016/j.tet.2012.11.084

  日期：2013.2

  The first biomimetic semisynthesis of goniomitine has been accomplished in nine steps with 11% overall yield starting from vincadifformine. Natural (-)- and unnatural (+)-goniomitine were prepared from (+)- and (-)-vincadifformine, respectively. The evaluation of the antiproliferative effect of both enantiomers proved unnatural (+)-goniomitine to be more potent, but this enantiomer as well as some close derivatives displayed a moderate activity only. (c) 2012 Published by Elsevier Ltd.