4-(1-phenylallyl)morpholine

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4-(1-phenylallyl)morpholine
• 英文别名: N-(1'-phenyl-2'-propenyl)morpholine；(S)-4-(1-phenylallyl)morpholine；1-(1-phenyl-2-propenyl)morphine；4-[(1S)-1-phenylprop-2-enyl]morpholine
• 化学式: C₁₃H₁₇NO
• 分子量: 203.284
• InChiKey: KYCOHOVPRZPLEG-ZDUSSCGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  吗啉 、 碳酸,甲基1-苯基-2-丙烯基酯 在 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 bis[2-(4'-(R)-isopropyl-oxazolin-2'-yl)phenyl]phenylphosphine 作用下， 以 乙腈 为溶剂， 反应 12.0h， 以86%的产率得到4-(1-phenylallyl)morpholine
  参考文献：
  名称：

  Rh（I）/ Bisoxazolinephosphine催化的区域和对映选择性烯丙基取代

  摘要：

  铑（I）/双恶唑啉膦组合已被开发为通用催化剂，可实现支链消旋烯丙基碳酸酯中各种氮，碳，氧和硫亲核试剂的动态动力学不对称烯丙基化。在中性条件下可以获得独家的分支选择性和高达99％的对映体过量。线性烯丙基底物（Z和E）也可以转化为具有出色的区域选择性和对映选择性的相同手性支链产物。分离并表征了手性π-烯丙基-Rh（III）/ NPN中间体，以了解高选择性的起源。

  DOI：

  10.1021/acscatal.0c00712

文献信息

• Sequential Catalytic Isomerization and Allylic Substitution. Conversion of Racemic Branched Allylic Carbonates to Enantioenriched Allylic Substitution Products
  作者：Shashank Shekhar、Brian Trantow、Andreas Leitner、John F. Hartwig

  DOI：10.1021/ja0644273

  日期：2006.9.1

  A catalytic protocol for the conversion of readily accessible racemic, branched aromatic allylic esters to branched allylic amines, ethers, and alkyls has been developed. Palladium-catalyzed isomerization of branched allylic esters to terminal allylic esters, followed by sequential iridium-catalyzed allylic substitution, gave the branched allylic products in good yield with high regioisomeric and enantiomeric

  已经开发了一种用于将容易获得的外消旋、支链芳族烯丙酯转化为支链烯丙胺、醚和烷基的催化方案。钯催化的支链烯丙基酯异构化为末端烯丙基酯，然后依次进行铱催化的烯丙基取代，以良好的收率得到支链烯丙基产物，具有高区域异构和对映异构选择性。富电子和缺电子支化烯丙基酯均产生 >90% ee 的产物。对于来自乙酸2-噻吩酯和碳酸二烯酯的反应的产物，也观察到高对映体过量。
• Rhodium-Catalyzed Enantioselective Hydroamination of Alkynes with Indolines
  作者：Qing-An Chen、Zhiwei Chen、Vy M. Dong

  DOI：10.1021/jacs.5b05200

  日期：2015.7.8

  alkynes via tandem rhodium catalysis gives branched N-allylic indolines with high regio- and enantioselectivity. An acid switch provides access to the linear isomer in preference to the branched isomer by an isomerization mechanism. Mechanistic studies suggest formation of an allene intermediate, which undergoes hydroamination to generate allylic amines instead of the enamine or imine products typically observed

  通过串联铑催化对内部炔烃进行加氢胺化得到具有高区域选择性和对映选择性的支链 N-烯丙基二氢吲哚。酸开关通过异构化机制提供了获得线性异构体优先于支化异构体的途径。机理研究表明形成了丙二烯中间体，该中间体经过加氢胺化生成烯丙胺，而不是通常在炔烃加氢胺化中观察到的烯胺或亚胺产物。
• Iridium-Catalyzed, Asymmetric Amination of Allylic Alcohols Activated by Lewis Acids
  作者：Yasuhiro Yamashita、Apsara Gopalarathnam、John F. Hartwig

  DOI：10.1021/ja0730718

  日期：2007.6.1

  enantioselective amination of allylic alcohols with Lewis acid activators to form branched allylic amine products is reported. The reactions of arylamines, benzylic amines, and secondary aliphatic amines in the presence of Nb(OEt)5 as activator occurred with high regioselectivities and high enantioselectivities. These results led to the development of Ir-catalyzed reactions of allylic alcohol with arylamines

  报道了烯丙醇与路易斯酸活化剂的直接、Ir 催化、区域和对映选择性胺化反应，形成支链烯丙胺产物。在 Nb(OEt)5 作为活化剂存在下，芳胺、苄胺和脂肪仲胺的反应具有高区域选择性和高对映选择性。这些结果导致了烯丙醇与芳胺和 BPh3 作为催化量的活化剂的 Ir 催化反应的发展。这些反应是烯丙醇对映选择性取代的罕见例子。它们是烯丙醇取代以从单取代烯丙醇产生支化取代产物以及烯丙醇与胺亲核试剂的对映选择性取代的特别不寻常的例子。
• Ir-catalyzed asymmetric allylic amination using chiral diaminophosphine oxides
  作者：Tetsuhiro Nemoto、Tatsurou Sakamoto、Takayoshi Matsumoto、Yasumasa Hamada

  DOI：10.1016/j.tetlet.2006.10.003

  日期：2006.12

  An Ir-catalyzed asymmetric allylic amination using chiral diaminophosphine oxide is described. Asymmetric allyno amination of terminal allylic carbonates proceeded in the presence of 2 mol % of Ir catalyst, 2 mol % of chiral diaminophosphine oxide, 5 mol % of NaPF6, and BSA, affording the chiral branched allylic amines in up to 95% cc. (c) 2006 Elsevier Ltd. All rights reserved.
• Ruthenium-Catalyzed Regio- and Enantioselective Allylic Amination of Racemic 1-Arylallyl Esters
  作者：Motoi Kawatsura、Kenta Uchida、Shou Terasaki、Hiroaki Tsuji、Maki Minakawa、Toshiyuki Itoh

  DOI：10.1021/ol5002768

  日期：2014.3.7

  The regio- and enantioselective allylic amination of racemic monosubstituted allylic esters, such as 1-arylallyl acetates, with cyclic secondary amines has been accomplished. The RuCl3/(S,S)-ip-pybox catalyst system has effectively catalyzed the reaction to afford the enantiomerically enriched branch-type allylic amines with perfect regioselectivity and high enantioselectivity.