tert-butyl (S)-2-[(diphenylmethylene)amino]pent-4-ynoate | 326667-54-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: tert-butyl (S)-2-[(diphenylmethylene)amino]pent-4-ynoate
• 英文别名: tert-butyl 2-(diphenylmethyleneamino)pent-4-ynoate；tert-butyl (2S)-2-(benzhydrylideneamino)pent-4-ynoate
• CAS: 326667-54-3
• 化学式: C₂₂H₂₃NO₂
• 分子量: 333.43
• InChiKey: FKXPHWNYZONMJI-IBGZPJMESA-N

物化性质

• 沸点：
  432.3±45.0 °C(Predicted)
• 密度：
  0.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  25
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tert-butyl (S)-2-[(diphenylmethylene)amino]pent-4-ynoate 在 水 、 potassium carbonate 、 三乙胺 、 三氟乙酸 、 柠檬酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 31.0h， 生成
  参考文献：
  名称：

  Synthesis and biological evaluation of triazole analogues of antillatoxin

  摘要：

  Antillatoxin 1, a cyclic lipopeptide, is known as an activator of voltage-gated sodium channels and exhibits potent neurotoxicity toward Neuro 2a mouse neuroblastoma cells. To investigate the biological effects of the side-chain structures at C5 and C5' in detail, we planned SAR studies of C5- and C5'-modified antillatoxin analogues. To diversify the structures at the last step of the synthesis, two key intermediates 4 and 6 possessing terminal alkynes at the C5- and C5'-positions were designed and synthesized using two distinct strategies. Sixteen side-chain derivatives were then prepared from 4 and 6 by coupling with a wide variety of azides via click chemistry, and subjected to the cytotoxicity assay. Although almost all of the C5-substituted analogues exhibited no cytotoxicity, the C5'-substituted analogues showed modest cytotoxicity. These results showed that C5' is more tolerant than C5 to structural modifications. The present SAR study will provide valuable information for designing new antillatoxin-based molecular probes for neuroscience research. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.05.012
• 作为产物：
  描述：

  二苯甲酮亚胺 在 4,4-dibutyl-2,6-bis-(3,4,5-trifluoro-phenyl)-4,5-dihydro-3H-4-azonia-cyclohepta[2,1-a;3,4-a']dinaphthalene 、 potassium hydroxide 作用下， 以 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 28.0h， 生成 tert-butyl (S)-2-[(diphenylmethylene)amino]pent-4-ynoate
  参考文献：
  名称：

  Dansylated Polytheonamide 模拟物的设计、合成和功能分析：一种人工肽离子通道

  摘要：

  我们在此报告了一种新型人工离子通道分子的设计、全合成和功能分析，称为丹磺酰化聚乙醇酰胺模拟物 (3)。通道 3 的设计基于一种非常有效的细胞毒素，polytheonamide B (1)。我们开发合成离子通道的策略可以很容易地衍生出各种功能，涉及两个关键特征。首先，通过用市售氨基酸替换许多需要多步合成的非蛋白质氨基酸残基来简化 1 的结构，同时保留折叠所需的那些残基。它显着减少了合成步骤的数量，并促进了 3 的实用化学构建。 其次，在残基 44 处引入炔丙基甘氨酸使得能够轻松安装丹酰基作为 3 膜定位的报告基因。新设计的保护基策略的应用提供了通过一个自动固体有效构建残基 12-48 的 37 个氨基酸序列相肽合成。从树脂上裂解肽后，通过丹酰基引入和与残基 1-11 的一个片段偶联反应合成 3，然后进行全局脱保护。简化的模拟 3 对 p388 小鼠白血病细胞 (IC(50) = 12 nM)

  DOI：

  10.1021/ja303831a

文献信息

• Evidence of the Electronic Factor for the Highly Enantioselective Catalytic Efficiency of <i>Cinchona</i>-Derived Phase-Transfer Catalysts
  作者：Mi-Sook Yoo、Byeong-Seon Jeong、Jeong-Hee Lee、Hyeung-geun Park、Sang-sup Jew

  DOI：10.1021/ol050123u

  日期：2005.3.1

  evaluated as phase-transfer catalysts in the enantioselective alkylation of glycine imine ester 1. The N-oxypyridine and cyanobenzene moieties might play an important role to form a rigid conformation by coordinating with H(2)O via hydrogen bonding leading to high enantioselectivity (97 approximately >99% ee), which provides evidence of an electronic factor for the high enantioselective catalytic efficiency

  [结构：见正文]制备了含有2'-N-氧吡啶和2'-氰基苯部分的金鸡纳生物碱衍生的季铵盐，并将其作为甘氨酸亚胺酯1的对映选择性烷基化反应中的相转移催化剂进行了评估。氰基苯部分可能起重要作用，通过氢键与H（2）O配合形成刚性构象，从而导致高对映选择性（97约> 99％ee），这为高对映选择性催化效率提供了电子因素的证据在相转移烷基化中。
• Counter-rotatable dual cinchona quinuclidinium salts and their phase transfer catalysis in enantioselective alkylation of glycine imines
  作者：Jiin Oh、Jihyeon Park、Keepyung Nahm

  DOI：10.1039/d1cc02785a

  日期：——

  Dual cinchona quinuclidinium salts with a diphenyl ether linker were synthesized and used as powerful asymmetric phase transfer catalysts in the α-alkylation of imines of glycine and alanine ester with 0.01–0.1 mol% loading (17 examples, 92–99% ee). Skewed conformers of dual quinuclidiniums at TS were proposed to rationalize their high efficiency via DFT calculations.

  合成了具有二苯醚接头的双金鸡纳奎宁鎓盐，并将其用作强大的不对称相转移催化剂，用于甘氨酸和丙氨酸酯亚胺的 α-烷基化，负载量为 0.01-0.1 mol%（17 个实例，92-99% ee）。提出了 TS 双 quinuclidinium 的倾斜构象异构体，以通过DFT 计算使其高效率合理化。
• Development of new asymmetric two-center catalysts in phase-transfer reactions
  作者：Tomoyuki Shibuguchi、Yuhei Fukuta、Yoko Akachi、Akihiro Sekine、Takashi Ohshima、Masakatsu Shibasaki

  DOI：10.1016/s0040-4039(02)02416-4

  日期：2002.12

  A new asymmetric two-center phase-transfer catalyst was designed and a catalyst library containing more than 40 new two-center catalysts was constructed. The catalysts were applied in phase-transfer alkylations and Michael additions to afford the corresponding products in up to 93% ee and 82% ee, respectively.

  设计了一种新的不对称两中心相转移催化剂，并建立了包含40多种新的两中心催化剂的催化剂库。将催化剂用于相转移烷基化和迈克尔加成中，以分别提供至多93％ee和82％ee的相应产物。
• Enantioselective Syntheses of Aeruginosin 298-A and Its Analogues Using a Catalytic Asymmetric Phase-Transfer Reaction and Epoxidation
  作者：Takashi Ohshima、Vijay Gnanadesikan、Tomoyuki Shibuguchi、Yuhei Fukuta、Tetsuhiro Nemoto、Masakatsu Shibasaki

  DOI：10.1021/ja037290e

  日期：2003.9.1

  We developed a versatile synthetic process for aeruginosin 298-A as well as several attractive analogues, in which all stereocenters were controlled by a catalytic asymmetric phase-transfer reaction and epoxidation. Furthermore, drastic counteranion effects in phase-transfer catalysis were observed for the first time, making it possible to three-dimensionally fine-tune the catalyst (ketal part, aromatic

  我们开发了一种通用的铜绿素 298-A 合成工艺以及几种有吸引力的类似物，其中所有立体中心都由催化不对称相转移反应和环氧化控制。此外，首次观察到相转移催化中强烈的反阴离子效应，使得对催化剂（缩酮部分、芳香部分和反阴离子）进行三维微调成为可能。
• A New<i>N</i>-Spiro C₂-Symmetric Chiral Quaternary Ammonium Bromide Consisting of 4,6-Disubstituted Biphenyl Subunit as an Efficient Chiral Phase-Transfer Catalyst
  作者：Keiji Maruoka、Takashi Ooi、Yasushi Kubota

  DOI：10.1055/s-2003-41478

  日期：——

  A new N-spiro chiral quaternary ammonium bromide has been designed and assembled from optically active 4,6-disubstituted biphenyl subunits. Its utility as an efficient chiral phase-transfer catalyst has been clearly demonstrated by application to the highly enantioselective alkylation of tert-butyl glycinate benzophenone Schiff base.

  一种新的 N-螺手性季铵溴化物已被设计并由光学活性 4,6-二取代联苯亚单元组装而成。通过应用于甘氨酸叔丁酯二苯甲酮席夫碱的高度对映选择性烷基化，已清楚地证明了其作为有效手性相转移催化剂的实用性。