N-crotylmorpholine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 恶嗪烷类
• 英文名称: N-crotylmorpholine
• 英文别名: (Z)-N-but-2-enyl morpholine；4-[(Z)-but-2-enyl]morpholine
• 化学式: C₈H₁₅NO
• 分子量: 141.213
• InChiKey: WLFHYEOSOUETLN-IHWYPQMZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  丙酰氯 、 N-crotylmorpholine 在 四氯化钛 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 8.0h， 以74%的产率得到rac-(2S,3S)-2,3-dimethyl-1-morpholinopent-4-en-1-one
  参考文献：
  名称：

  Lewis acid-catalyzed claisen rearrangement in the preparation of chiral products

  摘要：

  提供了一种新的Claisen重排反应。像烯丙胺、烯丙醚或烯丙硫醚等烯丙基反应物与酸氯化物在存在由Lewis酸和从三级胺和非氮碱组成的碱所选的Lewis酸催化剂组合的情况下发生反应。反应产物的立体化学可通过烯丙基反应物上取代基的位置和大小轻松控制。该反应可以在固体支持物上进行，即在适用于进行固相化学反应的基质表面上进行。

  公开号：

  US06359174B1
• 作为产物：
  描述：

  4-(2,2,2-trichloro-ethyl)-morpholine 、 乙基锂 以31%的产率得到
  参考文献：
  名称：

  TAKAMATSU, MASANORI;TERAO, YOSHIYASU;SEKIYA, MINORU, CHEM. AND PHARM. BULL., 1982, 30, N 8, 2682-2687

  摘要：

  DOI：

文献信息

• Phosphorus Functionalized Dendrimers and Hyperbranched Polymers: Is There a Need for Perfect Dendrimers in Catalysis?
  作者：Fabrizio Ribaudo、Piet W. N. M. Van Leeuwen、Joost N. H. Reek

  DOI：10.1560/ijc.49.1.79

  日期：2009.5

  In this paper we describe the facile and straightforward covalent functionalization of commercially available dendritic poly(propylenimine) and hyper‐branched poly(ethylenimine) with P‐containing functional groups. The P‐functionalized macromolecules have been applied as multivalent ligands in the Pd‐catalyzed allylic substitution reactions (batch and continuous process) using either morpholine or thiophenol as nucleophile. Palladium complexes of all described molecules are active in allylic substitution reactions. The PEI functionalized polymers appear more sensitive to small changes in the P/Pd ratio than the PPI analogues, but form catalysts that are more active. When used in a continuous flow process the macromolecules are completely retained by the nanofiltration membrane, while the catalytic activity decreases with time because of palladium depletion. This is more severe for the allylic thiolation, probably because of the stronger affinity of sulfur for palladium, facilitating palladium leaching.

  摘要 本文介绍了用含 P 的官能团对市售树枝状聚（丙烯亚胺）和超支化聚（乙烯亚胺）进行简便直接的共价官能化。含 P 官能团的大分子已作为多价配体应用于以吗啉或噻吩酚为亲核体的钯催化烯丙基取代反应（间歇和连续过程）中。所有所述分子的钯配合物在烯丙基取代反应中都很活跃。与 PPI 类似物相比，PEI 功能化聚合物似乎对 P/Pd 比率的微小变化更为敏感，但形成的催化剂活性更高。在连续流工艺中使用时，大分子会被纳滤膜完全截留，而催化活性则会随着时间的推移而降低，这是因为钯耗竭的缘故。烯丙基硫醇化的情况更为严重，这可能是因为硫与钯的亲和力更强，有利于钯的沥滤。
• N-Heterocyclic Carbene C,S Palladium(II) π-Allyl Complexes: Synthesis, Characterization, and Catalytic Application In Allylic Amination Reactions
  作者：Deepa Krishnan、Meiyi Wu、Minyi Chiang、Yongxin Li、Pak-Hing Leung、Sumod A. Pullarkat

  DOI：10.1021/om400110t

  日期：2013.4.22

  carbene C,S palladium(II) π-allyl complexes were successfully developed and characterized. Structural analyses of these complexes revealed that the organopalladium chelates adopt a skew-envelope conformation with a trans disposition of the substituents on the metal chelate rings. Utilizing these C,S palladium(II) π-allyl complexes as catalysts, a catalytic system for the allylic amination reaction has

  成功开发并表征了一系列五元N-杂环卡宾C，S钯（II）π-烯丙基配合物。对这些配合物的结构分析表明，有机钯螯合物采用偏斜包络构象，且金属螯合物环上的取代基发生转位。利用这些C，S钯（II）π-烯丙基络合物作为催化剂，已经开发出用于烯丙基胺化反应的催化体系。胺与不对称取代的烯丙基碳酸酯之间的一系列C–N键形成可通过区域选择性方式的复杂（±）-9高效催化。
• Reshuffle Bonds by Ball Milling: A Mechanochemical Protocol for Charge-Accelerated Aza-Claisen Rearrangements
  作者：Christian Schumacher、Lieselotte Fritz、Lena M. Hanek、Vitali Sidorin、Daniel Brüx、Carsten Bolm

  DOI：10.3390/molecules28020807

  日期：——

  This study presents the development of a mechanochemical protocol for a charge-accelerated aza-Claisen rearrangement. The protocol waives the use of commonly applied transition metals, ligands, or pyrophoric Lewis acids, e.g., AlMe3. Based on (heterocyclic) tertiary allylamines and acyl chlorides, the desired tertiary amides were prepared in yields ranging from 17% to 84%. Moreover, the same protocol was applied for a Belluš–Claisen-type rearrangement resulting in the synthesis of a 9-membered lactam without further optimization.

  本研究介绍了一种用于电荷加速氮-克莱森重排的机械化学方案。该方案无需使用常用的过渡金属、配体或发火路易斯酸（如 AlMe3）。以（杂环）叔烯丙基胺和酰基氯为基础，制备出了所需的叔酰胺，收率在 17% 到 84% 之间。此外，在贝鲁什-克莱森（Belluš-Claisen）型重排中也采用了相同的方案，无需进一步优化即可合成 9 元内酰胺。
• Using NMR to determine the relative stereochemistry of 7,7-diaryl-8,8′-dimethylbutan-1-ol lignans
  作者：Samuel J. Davidson、Claire E. Rye、David Barker

  DOI：10.1016/j.phytol.2015.09.014

  日期：2015.12

  Due to their linear, freely rotatable, structure many natural 7,7-diaryl-8,8'-dimethylbutan-7'-ol lignans are reported without any stereochemical assignment. Analysis of synthetic 8,8'-dimethylbutanol lignans and analogues reveals significant differences between the NMR data of syn-and anti-isomers. This information was then used to determine the relative stereochemistry of the C-8 and C-8' methyl groups in previously undefined natural products. (C) 2015 Phytochemical Society of Europe. Published by Elsevier B.V. All rights reserved.
• SILVERMAN G. S.; STRICKLAND S.; NICHOLAS K. M., ORGANOMETALLICS, 5,(1986) N 10, 2117-2124
  作者：SILVERMAN G. S.、 STRICKLAND S.、 NICHOLAS K. M.

  DOI：——

  日期：——