tert-butyl (E)-2-(2-methoxy-2-oxoethylidene)pyrrolidine-1-carboxylate | 223118-68-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: tert-butyl (E)-2-(2-methoxy-2-oxoethylidene)pyrrolidine-1-carboxylate
• 英文别名: tert-butyl (2E)-2-(2-methoxy-2-oxoethylidene)pyrrolidine-1-carboxylate
• CAS: 223118-68-1
• 化学式: C₁₂H₁₉NO₄
• 分子量: 241.287
• InChiKey: BRIIQLPCSMAAPI-CMDGGOBGSA-N

物化性质

• 沸点：
  325.3±42.0 °C(Predicted)
• 密度：
  1.181±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tert-butyl (E)-2-(2-methoxy-2-oxoethylidene)pyrrolidine-1-carboxylate 在 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate (S,S)-1,3-dimethyl-4,5-(Ph₂PCH₂)2-imidazolidin-2-one 、 氢气 作用下， 以 二氯甲烷 为溶剂， 20.0 ℃ 、101.32 kPa 条件下， 反应 12.0h， 生成 (S)-2-(2-吡咯烷基)乙酸甲酯 、 (R)-2-(2-吡咯烷基)乙酸甲酯
  参考文献：
  名称：

  Asymmetric synthesis of homoproline derivatives via Rh(I)-catalyzed hydrogenation using chiral bisphosphines as ligands

  摘要：

  It has been demonstrated for the first time that Rh(I)-catalyzed asymmetric hydrogenation of cyclic beta-enamino acid derivatives I using chiral bisphosphines could be a highly efficient synthetic method for optically active homoproline derivatives. The enantioselectivity and conversion yield were largely dependent upon the chiral ligand. Using the Me-BDPMI forming a seven-membered metal chelate, the N-acetylated beta-enamino acid methyl ester la was hydrogenated to give optically active homoproline derivative 2a with 100% conversion and 96% ee. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.04.014
• 作为产物：
  描述：

  methyl (E)-6-((tert-butoxycarbonyl)((pentafluorobenzoyl)oxy)amino)hex-2-enoate 在 tris-(dibenzylideneacetone)dipalladium(0) 、 1,3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以95%的产率得到tert-butyl (E)-2-(2-methoxy-2-oxoethylidene)pyrrolidine-1-carboxylate
  参考文献：
  名称：

  吡咯烷和哌啶的配体启用的氮杂-赫克环化和 N-(五氟苯甲酰氧基)氨基甲酸酯的级联

  摘要：

  描述了N-（五氟苯甲酰氧基）氨基甲酸酯的配体启用的 aza-Heck 环化和级联。这些研究包括第一个有效的无偏 6 - exo aza-Heck 环化的例子。该方法提供了对氨基甲酸酯保护的吡咯烷和哌啶的直接和灵活的访问。

  DOI：

  10.1002/anie.201801109

文献信息

• Reaction of thioamides with zinc enolate: Synthesis of vinylogous carbamates
  作者：Hyeon Kyu Lee、Jia Kim、Chwang Siek Pak

  DOI：10.1016/s0040-4039(99)00141-0

  日期：1999.3

  Eschenmoser sulfur extrusion reaction is failed to produce vinylogous carbamate II from N-(t-Boc)pyrrolidine-2-thion I but, treatment of methyl bromozincacetate with N-(t-Boc)pyrrolidine-2-thion I afforded good yield of vinylogous carbamate II. This thio-Reformatsky reaction appeared to be sensitive to the structure of substrates i.e. ring size or N-protecting groups. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Pyrrolidines and Piperidines by Ligand-Enabled Aza-Heck Cyclizations and Cascades of <i>N</i> -(Pentafluorobenzoyloxy)carbamates
  作者：Ian R. Hazelden、Rafaela C. Carmona、Thomas Langer、Paul G. Pringle、John F. Bower

  DOI：10.1002/anie.201801109

  日期：2018.4.23

  Ligand‐enabled aza‐Heck cyclizations and cascades of N‐(pentafluorobenzoyloxy)carbamates are described. These studies encompass the first examples of efficient non‐biased 6‐exo aza‐Heck cyclizations. The methodology provides direct and flexible access to carbamate protected pyrrolidines and piperidines.

  描述了N-（五氟苯甲酰氧基）氨基甲酸酯的配体启用的 aza-Heck 环化和级联。这些研究包括第一个有效的无偏 6 - exo aza-Heck 环化的例子。该方法提供了对氨基甲酸酯保护的吡咯烷和哌啶的直接和灵活的访问。
• Asymmetric synthesis of homoproline derivatives via Rh(I)-catalyzed hydrogenation using chiral bisphosphines as ligands
  作者：Yong Jian Zhang、Jung Hwan Park、Sang-gi Lee

  DOI：10.1016/j.tetasy.2004.04.014

  日期：2004.7

  It has been demonstrated for the first time that Rh(I)-catalyzed asymmetric hydrogenation of cyclic beta-enamino acid derivatives I using chiral bisphosphines could be a highly efficient synthetic method for optically active homoproline derivatives. The enantioselectivity and conversion yield were largely dependent upon the chiral ligand. Using the Me-BDPMI forming a seven-membered metal chelate, the N-acetylated beta-enamino acid methyl ester la was hydrogenated to give optically active homoproline derivative 2a with 100% conversion and 96% ee. (C) 2004 Elsevier Ltd. All rights reserved.