(S)-3-(1H-Indol-3-yl)-2-[3-methyl-but-2-en-(E)-ylideneamino]-propionic acid methyl ester | 78946-98-2

• 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: (S)-3-(1H-Indol-3-yl)-2-[3-methyl-but-2-en-(E)-ylideneamino]-propionic acid methyl ester
• 英文别名: methyl (2S)-3-(1H-indol-3-yl)-2-(3-methylbut-2-enylideneamino)propanoate
• CAS: 78946-98-2
• 化学式: C₁₇H₂₀N₂O₂
• 分子量: 284.358
• InChiKey: SLWQGVZECRYXAX-INIZCTEOSA-N

物化性质

• 沸点：
  458.7±45.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-3-(1H-Indol-3-yl)-2-[3-methyl-but-2-en-(E)-ylideneamino]-propionic acid methyl ester 在 palladium diacetate 、 sodium tetrahydroborate 、 氧气 、 溶剂黄146 、 二乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 23.0 ℃ 、101.33 kPa 条件下， 反应 3.5h， 生成
  参考文献：
  名称：

  A Short Synthetic Route to (+)-Austamide, (+)-Deoxyisoaustamide, and (+)-Hydratoaustamide from a Common Precursor by a Novel Palladium-Mediated Indole → Dihydroindoloazocine Cyclization

  摘要：

  The first synthesis of (+)-austamide (1), (+)-deoxyisoaustamide (2), and (+)-hydratoaustamide (10) by a very direct route is described (Scheme 1). Starting from tryptophan methyl ester (3) intermediate 5 is generated in two steps in >98% overall yield. The key step in the synthesis is a novel cyclization of 5 involving organopalladium intermediates which gives the dihydroazocine 6. From this key intermediate the target structures are accessible in just a few steps as shown in Scheme 1. The remarkable conversion of 5 --> 6 can be rationalized by the mechanistic pathway shown in Scheme 2 that involves a multistep sequence which includes palladation, cyclization, and rearrangement.

  DOI：

  10.1021/ja026663t
• 作为产物：
  描述：

  3-甲基-2-丁烯醛 、 L-色氨酸甲酯 生成 (S)-3-(1H-Indol-3-yl)-2-[3-methyl-but-2-en-(E)-ylideneamino]-propionic acid methyl ester
  参考文献：
  名称：

  3-甲基丁-2-烯醛与色胺及其衍生物的反应。对生物合成奥斯丁的建议

  摘要：

  色胺和3-甲基丁-2-烯醛提供了共轭亚胺3b，其与吡啶-甲苯磺酰氯环化，得到N-甲苯磺酰基-四氢-β-咔啉10; 或者，在pH 6.2的水性缓冲液中，形成了羟基异丁基衍生物9b。讨论了L-色氨酸甲酯与相同醛的反应以及这些研究可能的生物合成相关性。

  DOI：

  10.1016/s0040-4039(01)92944-2

文献信息

• Tremorgenic mycotoxins: synthesis of 6-demethoxyfumitremorgin C
  作者：Gerard J. O'Malley、Michael P. Cava

  DOI：10.1016/s0040-4039(00)95307-3

  日期：1987.1

  studies directed toward the development of a general route to the fumitremorgin group of mycotoxins are disclosed. A chloroformate-induced cyclization of a L-tryptophan imine afforded a 1,2,3,4-tetrahydro-β-carboline which was elaborated to 6-demethoxyfumitremorgin C.

  公开了针对开发真菌毒素的烟曲霉菌素组的一般途径的合成研究。L-色氨酸亚胺的氯甲酸酯诱导的环化反应提供了1,2,3,4-四氢-β-咔啉，其被精制为6-去甲氧基Fumitremorgin C.
• The reaction of 3-methylbut-2-enal with tryptamine and its derivatives. A suggestion for the biosynthesis of austamide
  作者：David M. Harrison

  DOI：10.1016/s0040-4039(01)92944-2

  日期：1981.1

  3-methylbut-2-enal furnished the conjugated imine 3b which cyclised with pyridine-tosyl chloride to yield the N-tosyl-tetrahydro-β-carboline 10; alternatively in pH 6.2 aqueous buffer the hydroxyisobutyl derivative 9b was formed. The reaction of L-tryptophan methyl ester with the same aldehyde and the possible biosynthetic relevance of these studies are discussed.

  色胺和3-甲基丁-2-烯醛提供了共轭亚胺3b，其与吡啶-甲苯磺酰氯环化，得到N-甲苯磺酰基-四氢-β-咔啉10; 或者，在pH 6.2的水性缓冲液中，形成了羟基异丁基衍生物9b。讨论了L-色氨酸甲酯与相同醛的反应以及这些研究可能的生物合成相关性。
• A concise, efficient route to fumitremorgins
  作者：Patrick D Bailey、Philip J Cochrane、Katrin Lorenz、Ian D Collier、David P.J Pearson、Georgina M Rosair

  DOI：10.1016/s0040-4039(00)01899-2

  日期：2001.1

  Using the kinetically controlled Pictet-Spengler reaction, we have developed a three-step, diastereoselective and enantiospecific synthesis of the natural product demethoxy-fumitremorgin C in 21% overall yield. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Synthesis and Evaluation of Tryprostatin B and Demethoxyfumitremorgin C Analogues
  作者：Haishan Wang、Takeo Usui、Hiroyuki Osada、A. Ganesan

  DOI：10.1021/jm9905662

  日期：2000.4.1

  Tryprostatin B and demethoxyfumitremorgin C are fungal inhibitors of mammalian cell cycle progression at the G(2)/M transition. N-Alkyl derivatives of the L-TrP-L-Pro diketopiperazine were prepared as analogues of tryprostatin B, and two of these were more active than the natural product. A second series of cis- and trans-tetrahydro-beta-carbolines annulated to a diketopiperazine were prepared as analogues of demethoxyfumitremorgin C. The nature of the alkyl substituent, as well as its cis or trans relationship in the tetrahydro-beta-carboline ring, was found to have a significant effect on cytotoxic activity. Small cis-alkyl substituents fall into the demethoxyfumitremorgin C family, whereas bulky benzyl trans compounds appear to act via a different mechanism of action.
• Short, Enantioselective Total Synthesis of Okaramine N
  作者：Phil S. Baran、Carlos A. Guerrero、E. J. Corey

  DOI：10.1021/ja034491+

  日期：2003.5.1

  enantioselective total synthesis of a member of the okaramine family of bis-indole alkaloids, okaramine N (1), has been accomplished via intermediates 2-7, as outlined. The N-prenylated derivative of (S)-tryptophan methyl ester (2) was coupled with Fmoc-protected N-tert-prenylated tryptophan (3) to form the amide 4 in 70% yield. Pd(II)-mediated cyclization/rearrangement, a key step in the synthesis, transformed

  已通过中间体 2-7 完成了双吲哚生物碱 okaramine 家族成员 okaramine N (1) 的首次对映选择性全合成。(S)-色氨酸甲酯 (2) 的 N-异戊二烯化衍生物与 Fmoc 保护的 N-叔异戊二烯化色氨酸 (3) 偶联形成酰胺 4，产率为 70%。Pd(II) 介导的环化/重排是合成中的关键步骤，将 4 转化为吲哚氮辛 5 (44%)，在一步中脱保护和环化得到六环二酮哌嗪 6 (95%)。在以下新颖的关键序列中，6 转化为 1：(1) 与 N-甲基三唑啉二酮的选择性烯反应，(2) 剩余的叔异戊二烯化吲哚亚基光氧化以提供 7，以及 (3) 7 的热逆烯反应得到 okaramine N (70% from 6)。