1-chloro-4-((1-phenylallyl) oxy) benzene | 838828-15-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 1-chloro-4-((1-phenylallyl) oxy) benzene
• 英文别名: 1-chloro-4-((1-phenylallyl)oxy)benzene；1-phenyl-1-(4-chlorophenoxy)-2-propene；Benzene, 1-chloro-4-[(1-phenyl-2-propenyl)oxy]-；1-chloro-4-(1-phenylprop-2-enoxy)benzene
• CAS: 838828-15-2
• 化学式: C₁₅H₁₃ClO
• 分子量: 244.721
• InChiKey: VWIUOOHROPKGNF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  肉桂基氯 、 对氯苯酚 在 bis[dichloro(pentamethylcyclopentadienyl)ruthenium(III)] 、 potassium carbonate 作用下， 以 乙腈 为溶剂， 反应 16.33h， 以91%的产率得到1-chloro-4-((1-phenylallyl) oxy) benzene
  参考文献：
  名称：

  From precursor to catalyst: the involvement of [Ru(η5-Cp∗)Cl2]2 in highly branch selective allylic etherification of cinnamyl chlorides

  摘要：

  (RuCp*Cl-2)(2), a general entry into Cp*Ru sandwich and half-sandwich chemistry was first used as a precatalyst in allylic etherification of cinnamyl chlorides with up to 98:2 regioselectivity (19 examples). Both the solvent effect and the exsiccant reaction condition are crucial to the reactivity and selectivity. Preliminary mechanism studies and the demonstration of Fluoxetine synthesis were presented in this work as well. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2013.12.074

文献信息

• Synthesis and Reactivity of [Ru(Cp*)(L)(MeCN) ₂ ][PF ₆ ] (L = Ph ₂ POMe or Ph ₂ P‐ <i>o</i> ‐tolyl) and {Ru(Cp*)[Ph ₂ PCH ₂ C( <i>t</i> Bu)=O](MeCN)}[PF ₆ ] Complexes, Their Involvement as Catalyst Precursors for Regioselective Allylic Substitution Reactions and Related [Ru(Cp*)Cl(Ph ₂ POMe)(RCHCHCH ₂ )][PF ₆ ] η ³ ‐Allyl Ruthenium( <scp>IV</scp> ) Intermediates
  作者：Bernard Demerseman、Jean‐Luc Renaud、Loïc Toupet、Claudie Hubert、Christian Bruneau

  DOI：10.1002/ejic.200501051

  日期：2006.4

  The synthesis of the new complexes [Ru(Cp*)(L)(MeCN)2][PF6] (L = Ph2POMe or Ph2P-o-tolyl) and Ru(Cp*)[Ph2PCH2C(tBu)=O](MeCN)}[PF6] (2a–c) is achieved starting from [Ru(Cp*)(MeCN)3][PF6]. The acetonitrile ligands in complexes 2a–c are labile, as emphasised by the easy formation of Ru(Cp*)(CO)2[Ph2PCH2C(=O)tBu]}[PF6] (3). The keto-phosphane is used as a tool to convert 3 into Ru(Cp*)(CO)[Ph2PCH2C(tBu)=O]}[PF6]

  新配合物 [Ru(Cp*)(L)(MeCN)2][PF6]（L = Ph2POMe 或 Ph2P-o-tolyl）和 Ru(Cp*)[Ph2PCH2C(tBu)=O]( MeCN)}[PF6] (2a–c) 从 [Ru(Cp*)(MeCN)3][PF6] 开始实现。正如 Ru(Cp*)(CO)2[Ph2PCH2C(=O)tBu]}[PF6] (3) 的容易形成所强调的那样，配合物 2a-c 中的乙腈配体是不稳定的。酮磷烷用作将 3 转化为 Ru(Cp*)(CO)[Ph2PCH2C(tBu)=O]}[PF6] (5) 的工具。配合物 5 在作为溶剂的甲醇中与 1,1-二苯基-2-丙炔-1-醇反应以提供乙烯基-卡宾配合物 Ru(Cp*)(CO)[=C(OMe)CH=CPh2][Ph2PCH2C(= O)tBu]}[PF6]。新的 η3-烯丙基钌 (IV) 衍生物 [Ru(Cp*)Cl(
• Ruthenium-CatalyzedO-Allylation of Phenols from Allylic Chloridesvia Cationic[Cp*(η3-allyl)(MeCN)RuX][PF6] Complexes
  作者：Mbaye D. Mbaye、Bernard Demerseman、Jean-Luc Renaud、Loïc Toupet、Christian Bruneau

  DOI：10.1002/adsc.200404023

  日期：2004.6

  from the reaction of [Cp*(MeCN)3Ru][PF6] with allylic halides were identified as intermediate catalytic species. An X-ray structure determination of the complex [Cp*(MeCHCHCH2)(MeCN)RuBr][PF6] disclosed an (endo-trans-MeCHCHCH2) allylic ligand. The structural information obtained from the study of Cp*(allyl)Ru(IV) complexes indicated that electronic effects at the coordinated allylic ligand likely account

  [Cp *（MeCN）3 Ru（II）] [PF 6 ]配合物是在温和条件下在K 2 CO 3存在下酚与烯丙基氯化物进行O-烯丙基化的有效催化剂前体。该钌前体根据区域选择性反应提供支链的烯丙基芳基醚，这与来自相同底物的未催化亲核取代相反。稳定（η 3 -烯丙基）钌（IV）从的[Cp *（MeCN中）的反应得到的阳离子络合物3茹] [PF 6 ]与烯丙基卤化物被鉴定为中间体催化物种。络合物[Cp *（MeCHCHCH 2）（MeCN）RuBr] [PF的X射线结构测定图6 ]公开了（内-反-MeCHCHCH 2）烯丙基配体。从对Cp *（烯丙基）Ru（IV）配合物的研究中获得的结构信息表明，与脂肪族烯丙基氯相比，在烯丙基氯配体上的电子效应可能解释了从肉桂酰氯获得的更好的区域选择性。
• Regioselective allylic alkylation and etherification catalyzed by in situ generated N-heterocyclic carbene ruthenium complexes
  作者：Nevin Gürbüz、Ismail Özdemir、Bekir Çetinkaya、Jean-Luc Renaud、Bernard Demerseman、Christian Bruneau

  DOI：10.1016/j.tetlet.2005.11.051

  日期：2006.1

  chlorides by carbon nucleophiles and phenols, respectively. After generation of diaminocarbene species upon deprotonation by tBuOK, their association with [Cp*Ru(MeCN)3]PF6 induces a very high regioselectivity in favor of the branched isomers when cinnamyl derivatives are used as starting substrates. They also provide good regioselectivities for the allylation of phenols by unsymmetrical aliphatic allylic

  卤代苯并咪唑鎓盐首次用作配体前体，分别被碳亲核试剂和苯酚钌催化的烯丙基碳酸盐和氯化物取代。在通过t BuOK去质子化后生成二氨基卡宾物质后，当使用肉桂基衍生物作为起始底物时，它们与[Cp * Ru（MeCN）3 ] PF 6的缔合引起非常高的区域选择性，有利于支链异构体。它们还为苯酚通过不对称脂族烯丙基底物（如3-氯-4-苯基丁-1-烯）的烯丙基化提供了良好的区域选择性，因此可以直接获得新的烯丙基苯基醚。
• Regio- and Enantioselective Iridium-Catalyzed Intermolecular Allylic Etherification of Achiral Allylic Carbonates with Phenoxides
  作者：Fernando López、Toshimichi Ohmura、John F. Hartwig

  DOI：10.1021/ja029790y

  日期：2003.3.1

  An enantioselective and regioselective iridium-catalyzed allylic etherification is described. The reaction of sodium and lithium aryloxides with achiral (E)-cinnamyl and terminal aliphatic allylic electrophiles in the presence of 2 mol % of an iridium-phosphoramidite complex provides chiral allylic aryl ethers in high yields and excellent levels of regio- and enantioselectivity. Lithium aryloxides

  描述了对映选择性和区域选择性铱催化的烯丙基醚化。钠和锂芳基氧化物与非手性 (E)-肉桂基和末端脂肪族烯丙基亲电试剂在 2 mol% 的铱-亚磷酰胺络合物存在下反应，以高产率和出色的区域和对映选择性提供手性烯丙基芳基醚。在邻位、间位或对位包含单个取代基的芳基氧化锂以及位阻酚盐是可以接受的。THF 中的反应显示出最合适的速率、区域和对映选择性平衡。也观察到来自烷基 (E)-烯丙基碳酸酯反应的产物的高 ee。
• Enantioselective amination and etherification
  申请人：Hartwig F John

  公开号：US20060199728A1

  公开（公告）日：2006-09-07

  The present invention is directed to a catalyst composition, comprising: (1) a catalyst precursor having the general structure MSX n wherein M is a transition metal selected from the group consisting of iridium, molybdenum, and tungsten; S is a coordinating ligand; X is a counterion; and n is an integer from 0 to 5; and (2) a phosphoramidite ligand having the structure wherein O—C n —O is an aliphatic or aromatic diolate and wherein R 1 , R 2 , R 3 and R 4 are selected from the group consisting of substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted aliphatic groups, and combinations thereof, with the proviso that at least one of R 1 , R 2 , R 3 , or R 4 must be a substituted or unsubstituted aryl or heteroaryl group. The present invention is also directed to activated catalysts made from the above catalyst composition, as well as methods of allylic amination and etherification using the above catalysts.

  本发明涉及一种催化剂组合物，包括：（1）具有一般结构MSXn的催化剂前体，其中M是从铱、钼和钨组成的过渡金属中选择的；S是一个配位配体；X是一个计数离子；n是从0到5的整数；以及（2）具有以下结构的磷酰胺配体，其中O-Cn-O是脂肪族或芳香族二醇，其中R1、R2、R3和R4选自取代或未取代的芳基基团、取代或未取代的杂环基团、取代或未取代的脂肪基团和它们的组合，但至少有一个R1、R2、R3或R4必须是取代或未取代的芳基或杂环基团。本发明还涉及由上述催化剂组合物制备的活性催化剂，以及使用上述催化剂进行烯丙基胺化和醚化的方法。