(E)-tert-butyl 3-(3-methoxy-3-oxoprop-1-enyl)-1H-indole-1-carboxylate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: (E)-tert-butyl 3-(3-methoxy-3-oxoprop-1-enyl)-1H-indole-1-carboxylate
• 英文别名: (E)-tert-butyl 3-(3-methoxy-3-oxoprop-1-en-1-yl)-1H-indole-1-carboxylate；tert-butyl 3-[(E)-3-methoxy-3-oxo-prop-1-enyl]indole-1-carboxylate；tert-Butyl 3-(3-methoxy-3-oxopropen-1-yl)indole-1-carboxylate；tert-butyl 3-[(E)-3-methoxy-3-oxoprop-1-enyl]indole-1-carboxylate
• 化学式: C₁₇H₁₉NO₄
• 分子量: 301.342
• InChiKey: VSMVLFKTUMKNRW-MDZDMXLPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  57.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (E)-tert-butyl 3-(3-methoxy-3-oxoprop-1-enyl)-1H-indole-1-carboxylate 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 以76%的产率得到吲哚-3-丙烯酸甲酯
  参考文献：
  名称：

  Novel cyclo-dimerization of 1-tert-butoxycarbonyl-3-alkenylindole derivatives

  摘要：

  Reaction of 1-tert-butoxycarbonyl-3-cyclopentylidenemethyl-1H-indole with an excess of trifluoroacetic acid in dichloromethane at room temperature gave a cyclic dimer, 13-cyclopentyl-6,7,12,13-tetrahydrospiro[5H-cyclohepta[1,2-b:4,5-b(1)]di-indole-6,1'-cyclopentane] in 73% yield as the sole product through a novel cyclo-dimerization process. Structure of the cyclic dimer derived from 5-bromo-1-t-butoxycarbonyl-3-cyclopentylidenemethyl-1H-indole was elucidated by X-ray crystallographic analysis. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.12.072
• 作为产物：
  描述：

  反式吲哚-3-烯丙酸 在 potassium carbonate 作用下， 以 四氢呋喃 、 丙酮 为溶剂， 反应 72.0h， 生成 (E)-tert-butyl 3-(3-methoxy-3-oxoprop-1-enyl)-1H-indole-1-carboxylate
  参考文献：
  名称：

  Discovery of a Novel Series of Indolyl Hydrazide Derivatives as Diacylglycerol Acyltransferase‐1 Inhibitors

  摘要：

  研究人员合成了一系列新型酰肼衍生物，作为潜在的二酰基甘油酰基转移酶（DGAT）抑制剂。其中，化合物 8u 和 8v 具有选择性和强效的 DGAT-1 抑制活性。此外，化合物 8u 还能剂量依赖性地抑制 HepG2 细胞株中甘油三酯的合成。此外，用化合物 8u 进行口服脂质耐受性试验显示，与用车辆处理的对照组动物相比，血浆甘油三酯水平显著下降，这表明急性脂质挑战后甘油三酯的吸收延迟。

  DOI：

  10.1002/bkcs.10123

文献信息

• Catalytic Hydroetherification of Unactivated Alkenes Enabled by Proton‐Coupled Electron Transfer
  作者：Elaine Tsui、Anthony J. Metrano、Yuto Tsuchiya、Robert R. Knowles

  DOI：10.1002/anie.202003959

  日期：2020.7.13

  We report a catalytic, light‐driven method for the intramolecular hydroetherification of unactivated alkenols to furnish cyclic ether products. These reactions occur under visible‐light irradiation in the presence of an IrIII‐based photoredox catalyst, a Brønsted base catalyst, and a hydrogen‐atom transfer (HAT) co‐catalyst. Reactive alkoxy radicals are proposed as key intermediates, generated by direct

  我们报告了一种催化光驱动方法，用于未活化烯醇的分子内加氢醚化以提供环醚产品。这些反应在 Ir III基光氧化还原催化剂、布朗斯台德碱催化剂和氢原子转移 (HAT) 助催化剂存在下在可见光照射下发生。反应性烷氧基被认为是关键中间体，是通过质子耦合电子转移机制直接均裂激活醇 O−H 键而产生的。该方法表现出广泛的底物范围和高官能团耐受性，并且适应多种烯烃取代模式。还提出了证明该催化系统扩展到碳醚化反应的结果。
• Transition-Metal-Free Stereocomplementary Cross-Coupling of Diols with Boronic Acids as Nucleophiles
  作者：Víctor Ortega、Estefanía del Castillo、Aurelio G. Csákÿ

  DOI：10.1021/acs.orglett.7b03192

  日期：2017.11.17

  The transition-metal-free diastereoselective C(sp2)–C(sp3) cross-coupling between unprotected diols and boronic acids or potassium organotrifluoroborates is reported. Depending on the reaction conditions, the syn or the anti reaction products are obtained in a stereocomplementary fashion. This type of coupling is developed with alkenyl-, heteroaryl- and arylboron compounds as carbon nucleophiles.

  据报道，未保护的二醇与硼酸或有机三氟硼酸钾之间存在无过渡金属的非对映选择性C（sp 2）–C（sp 3）交叉偶联。取决于反应条件，以立体互补的方式获得顺式或反式反应产物。这种偶联是用烯基，杂芳基和芳基硼化合物作为碳亲核试剂开发的。
• Lithium Enolates in the Enantioselective Construction of Tetrasubstituted Carbon Centers with Chiral Lithium Amides as Noncovalent Stereodirecting Auxiliaries
  作者：Kai Yu、Ping Lu、Jeffrey J. Jackson、Thuy-Ai D. Nguyen、Joseph Alvarado、Craig E. Stivala、Yun Ma、Kyle A. Mack、Trevor W. Hayton、David B. Collum、Armen Zakarian

  DOI：10.1021/jacs.6b11673

  日期：2017.1.11

  Lithium enolates derived from carboxylic acids are ubiquitous intermediates in organic synthesis. Asymmetric transformations with these intermediates, a central goal of organic synthesis, are typically carried out with covalently attached chiral auxiliaries. An alternative approach is to utilize chiral reagents that form discrete, well-defined aggregates with lithium enolates, providing a chiral environment

  源自羧酸的锂烯醇化物是有机合成中普遍存在的中间体。这些中间体的不对称转化是有机合成的核心目标，通常使用共价连接的手性助剂进行。另一种方法是利用手性试剂与烯醇锂形成离散的、明确定义的聚集体，提供有利于不对称键形成的手性环境。这些试剂有效地充当非共价或无痕手性助剂。氨基锂是此类试剂的明显选择，因为已知它们会与烯醇锂形成混合聚集体。我们在这里证明了混合聚集体可以在几类反应中影响锂烯醇化物的高度对映选择性转化，最显着的是在形成四取代和季碳中心的转化中。通过水萃取轻松回收手性试剂是此一步协议的另一个实际优势。还报告了中心反应聚集体的晶体学、光谱学和计算研究，这些研究提供了对选择性起源的洞察。
• Direct Enantioselective Conjugate Addition of Carboxylic Acids with Chiral Lithium Amides as Traceless Auxiliaries
  作者：Ping Lu、Jeffrey J. Jackson、John A. Eickhoff、Armen Zakarian

  DOI：10.1021/ja512213c

  日期：2015.1.21

  Michael addition is a premier synthetic method for carbon-carbon and carbon-heteroatom bond formation. Using chiral dilithium amides as traceless auxiliaries, we report the direct enantioselective Michael addition of carboxylic acids. A free carboxyl group in the product provides versatility for further functionalization, and the chiral reagent can be readily recovered by extraction with aqueous acid. The method has been applied in the enantioselective total synthesis of the purported structure of pulveraven B.
• Novel cyclo-dimerization of 1-tert-butoxycarbonyl-3-alkenylindole derivatives
  作者：Ikuo Kawasaki、Masami Terano、Erika Yada、Miwa Kawai、Masayuki Yamashita、Shunsaku Ohta

  DOI：10.1016/j.tetlet.2004.12.072

  日期：2005.2

  Reaction of 1-tert-butoxycarbonyl-3-cyclopentylidenemethyl-1H-indole with an excess of trifluoroacetic acid in dichloromethane at room temperature gave a cyclic dimer, 13-cyclopentyl-6,7,12,13-tetrahydrospiro[5H-cyclohepta[1,2-b:4,5-b(1)]di-indole-6,1'-cyclopentane] in 73% yield as the sole product through a novel cyclo-dimerization process. Structure of the cyclic dimer derived from 5-bromo-1-t-butoxycarbonyl-3-cyclopentylidenemethyl-1H-indole was elucidated by X-ray crystallographic analysis. (C) 2004 Elsevier Ltd. All rights reserved.