(3S,4S)-1-benzyl-3,4-bis(methoxymethoxy)pyrrolidine | 137945-72-3

• 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: (3S,4S)-1-benzyl-3,4-bis(methoxymethoxy)pyrrolidine
• CAS: 137945-72-3
• 化学式: C₁₅H₂₃NO₄
• 分子量: 281.352
• InChiKey: AWRKWEOPBRJVQG-GJZGRUSLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  40.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3S,4S)-1-benzyl-3,4-bis(methoxymethoxy)pyrrolidine 在 palladium hydroxide - carbon 4-二甲氨基吡啶 、 氢气 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 25.0 ℃ 、101.33 kPa 条件下， 反应 18.0h， 生成 (2-aminophenyl)-[(3S,4S)-3,4-bis(methoxymethoxy)pyrrolidin-1-yl]methanone
  参考文献：
  名称：

  Exploratory Synthetic Studies of the α-Methoxylation of Amides via Cuprous Ion-Promoted Decomposition of o-Diazobenzamides

  摘要：

  A convenient nonelectrochemical amide oxidation method has been developed. The process involves a cuprous ion-promoted decomposition of o-diazobenzamides like 4, generated in situ from the corresponding o-aminobenzamides, to give N-acyliminium ion intermediate 9 via a 1,5-H-atom transfer, followed by metal-catalyzed oxidation of the resulting alpha-amidyl radical. The transformation produces alpha-methoxybenzamides 15 in good yields. An attempt was made to apply this oxidation method to a total synthesis of the alkaloid (-)-anisomycin (16). Scalemic o-aminobenzamide pyrrolidine derivatives 18a/18b underwent oxidation to give a-methoxylated amide substrates 19a/ 19b, respectively, in good yields. However, alkylation of the N-acyliminium intermediate 20 with (p-methoxybenzyl)magnesium chloride gave the undesired anti-compounds 22a/22b as the major products. The amide oxidation exhibits good regioselectivity with many unsymmetrical 2-substituted piperidine and pyrrolidine systems. In general, it appears that the larger the C-2 substituent, the greater the methylene/methine H-atom abstraction ratio. A mechanistic rationale for this selectivity is suggested based upon amide rotamer populations. An extension of this methodology can be used to conduct two sequential amide oxidations using readily prepared 2-amino-6-nitrobenzamides such as 68 and 69.

  DOI：

  10.1021/jo961529a
• 作为产物：
  描述：

  (-)-(2S,3S)-2,3-bis(methoxymethoxy)butane-1,4-diol 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 73.0h， 生成 (3S,4S)-1-benzyl-3,4-bis(methoxymethoxy)pyrrolidine
  参考文献：
  名称：

  使用官能化的环硝酮的环加成反应合成三羟基吡咯烷和吲哚并核苷，以及（+）-和（-）-龙胆草碱的合成

  摘要：

  3,4- isopropylidenedioxy-的环加成Δ 1吡咯啉-1-氧化物（9），（3小号，4小号）-3,4-二（甲氧基甲氧基） - Δ 1 -pyrroline- Ñ氧化物（28），和其（3 - [R，4 - [R ）-对映体，用适当官能化的烯烃已导致1,2,6- trihydroxypyrrolizidines的合成14,33和耳鼻喉科-33，和1,2,7- trihydroxyindolizidines 22,39和耳鼻喉科-39。在这些合成中，两个对映异构体中间体的脱氧导致制备了二羟基化的吲哚唑烷（+）-龙胆草碱及其（-）-对映体。

  DOI：

  10.1016/s0040-4020(98)00572-9

文献信息

• Improving cytotoxic properties of ferrocenes by incorporation of saturated N-heterocycles
  作者：Tomáš Hodík、Martin Lamač、Lucie Červenková Šťastná、Petra Cuřínová、Jindřich Karban、Hana Skoupilová、Roman Hrstka、Ivana Císařová、Róbert Gyepes、Jiří Pinkas

  DOI：10.1016/j.jorganchem.2017.06.005

  日期：2017.10

  selected ferrocene derivatives were determined by X-ray diffraction analysis. The ferrocene derivatives and the ruthenium complexes were tested in vitro for their cytotoxic properties against three cell lines derived from ovarian cancer (A2780, A2780cis, and SK-OV-3) and against non-tumour embryonic cell line HEK293 (human kidney cells). The most active ferrocene derivatives displayed cytotoxicity in submicromolar

  通式的二茂铁衍生物的家族的[Fe（η 5 -C 5 H ^ 4 CH 2（p -C 6 H ^ 4）CH 2（N-HET））2 ]轴承饱和六元和五元N-杂环（N-het）已准备好。所选择的配合物与酸（HCl，乙酸）的反应提供相应的盐酸盐或导致官能化的侧链N-杂环的脱保护。的[茹（η反应6 - p氯-cymene）2 } 2与相应的环戊二烯衍生物，得到的阳离子钌络合物的[Ru（η] 6- p -cymene）（η 5 -C 5 H ^ 4 CH 2（p -C 6 H ^ 4）CH 2（N-HET））]氯而ruthenocenes的[Ru（η 5 -C 5 H ^ 4 CH 2（p - C 6 H 4）CH 2（N-het））2形成副产物。通过元素分析，熔点，NMR和ESI-MS对制备的配合物（20个实施例）进行表征，并通过X射线衍射分析确定所选择的二茂铁衍生物的分子结构。二茂铁衍生物和钌配
• A nitrone-based approach to the enantioselective total synthesis of (-)-anisomycin
  作者：Roberto Ballini、Enrico Marcantoni、Marino Petrini

  DOI：10.1021/jo00030a051

  日期：1992.2
• Synthesis of Nitrones Using the Methyltrioxorhenium/Hydrogen Peroxide System
  作者：Robert W. Murray、Kaliappan Iyanar、Jianxin Chen、James T. Wearing

  DOI：10.1021/jo961252e

  日期：1996.11.15

  Secondary amines are oxidized by the methyltrioxorhenium/hydrogen peroxide system to the corresponding nitrones in excellent yield. The results provide a further example of the parallel between the chemistry of this metal system and that of the dioxiranes.