2-(1'-hydroxy-2'-methylbut-3'-enyl)phenol

• 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: 2-(1'-hydroxy-2'-methylbut-3'-enyl)phenol
• 英文别名: 2-(1-Hydroxy-2-methylbut-3-enyl)phenol
• 化学式: C₁₁H₁₄O₂
• 分子量: 178.231
• InChiKey: KZSJYTJPFGVXFP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  3-but-3-en-2-yl-1,1-dimethyl-3H-2,1-benzoxasilole 在 potassium fluoride 、 双氧水 作用下， 以68%的产率得到2-(1'-hydroxy-2'-methylbut-3'-enyl)phenol
  参考文献：
  名称：

  通过五价硅中间体的新型重排，新合成1,3-二氢苯并[1,2]恶唑。

  摘要：

  描述了一种新的苯并[1,2]恶唑的合成方法，其中发生了前所未有的分子内烯丙基转移，可能涉及五价硅中间体。

  DOI：

  10.1039/b311804e

文献信息

• Ionic Liquid-accelerated Allylation of Carbonyl Compounds with a Catalytic Amount of Indium Generated from In Situ Reduction of InCl₃with Aluminum
  作者：Tsunehisa Hirashita、Yuki Sato、Dai Yamada、Fusako Takahashi、Shuki Araki

  DOI：10.1246/cl.2011.506

  日期：2011.5.5

  In ionic liquids allylation of carbonyl compounds with a catalytic amount of indium(III) trichloride proceeds smoothly to give the corresponding homoallylic alcohol in the presence of aluminium. Th...

  在离子液体中，在铝存在下，羰基化合物与催化量的三氯化铟 (III) 的烯丙基化反应顺利进行，得到相应的高烯丙醇。这...
• Aqueous Barbier Allylation of Aldehydes Mediated by Tin
  作者：Ricardo Guimarães、Dimas Lima、Maria Barros、Lívia Cavalcanti、Fernando Hallwass、Marcelo Navarro、Lothar Bieber、Ivani Malvestiti

  DOI：10.3390/12092089

  日期：——

  The aqueous tin-mediated Barbier reaction affords good to excellent yields and moderate syn diastereoselectivity under basic and acidic conditions. The high yields and stereoselectivity observed in the case of o-substituted aldehydes suggest a cyclic organotin intermediate or transition state in K2HPO4 solution. A practical and efficient aqueous tin allylation of methoxy- and hydroxybenzaldehydes can be carried out in HCl solution in 15 minutes to afford the corresponding homoallylic alcohols in high yields. Aliphatic aldehydes give moderate to excellent yields with reaction times ranging from 30 to 60 minutes. Under these conditions, crotylation gives exclusively the γ-product and the syn isomer is formed preferentially. For 2-methoxybenzaldehyde, an equilibration of the isomers to a syn/anti ratio of 1:1 can be observed after several hours. Control experiments with radical sources or scavengers give no support for radical intermediates. NMR studies suggest a mechanism involving an organotin intermediate. The major organotin species formed depends on the reaction medium and the reaction time. The use of acidic solution reduces the reaction times, due to the acceleration of the formation of the allyltin(IV) species.

  水相锡介导的Barbier反应在碱性和酸性条件下可实现良好至优异的产率和适度的顺式二构体选择性。对于邻位取代的醛类所观察到的高产率和立体选择性表明在K₂HPO₄溶液中存在环状有机锡中间体或过渡态。在HCl溶液中，可以在15分钟内高效地实现甲氧基和羟基苯甲醛的水相锡烯丙基化反应，获得相应的同烯丙醇，产率很高。脂肪醛的产率在中等到优异之间，反应时间为30至60分钟。在这些条件下，克罗提化仅产生γ-产物，并且更偏向形成顺式异构体。对于2-甲氧基苯甲醛，经过几小时后可观察到异构体之间的平衡，顺/反的比例为1:1。使用自由基源或清除剂的对照实验并未支持自由基中间体的存在。核磁共振研究表明该反应机制涉及有机锡中间体。形成的主要有机锡物种依赖于反应介质和反应时间。使用酸性溶液可以缩短反应时间，这是由于促进了烯丙锡(IV)物种的形成。
• Regioselectivity in the intramolecular allyl transfer reaction catalysed by electrogenerated nickel complexes: influence of metal ions
  作者：Delphine Franco、Elisabet Duñach

  DOI：10.1016/s0040-4020(02)01184-5

  日期：2002.11

  carbonyl groups has been studied by electrosynthesis, in a nickel-catalysed reaction. The influence of metal ions such as Mg2+, Zn2+ and Al3+ has been examined. Regioselectivity towards the branched isomer was better with Zn2+ than with Mg2+ ions, but it was higher in the absence of added metal ions.

  在镍催化的反应中，已经通过电合成研究了烯丙基部分从取代的烯丙基芳基醚到羰基的分子内转移。研究了金属离子如Mg 2 +，Zn 2+和Al 3+的影响。Zn 2+相对于Mg 2+离子对支链异构体的区域选择性更好，但在不添加金属离子的情况下更高。
• A practical procedure of low valent tin mediated Barbier allylation of aldehydes in wet solvent
  作者：Conxín Vilanova、María Sánchez-Péris、Steven Roldán、Bhaskar Dhotare、Miguel Carda、Angshuman Chattopadhyay

  DOI：10.1016/j.tetlet.2013.09.096

  日期：2013.11

  Use of aluminium as the reducing metal in spontaneous bimetal redox reaction has been elegantly exploited for allylation/crotylation of aldehydes in wet solvent. Here, low valent tin was prepared in situ by reduction of SnCl2 center dot 2H(2)O with aluminium in THF/water. The resulting low valent tin acted as an efficient mediator for allylation and crotylation of aldehydes (3a-q) producing the corresponding homoallylic alcohols. The efficacy of this procedure was due to its operational simplicity, practical viability, inexpensiveness, good yields of the products and short reaction time. (C) 2013 Elsevier Ltd. All rights reserved.
• A new synthesis of 1,3-dihydrobenzo[1,2]oxasiloles by a novel rearrangement of a pentavalent silicon intermediate
  作者：George Bashiardes、Vanessa Chaussebourg、G�raldine Laverdan、Jacques Pornet

  DOI：10.1039/b311804e

  日期：——

  A new synthesis of benzo[1,2]oxasiloles is described, wherein an unprecedented intramolecular allylic transposition takes place probably involving a pentavalent silicon intermediate.

  描述了一种新的苯并[1,2]恶唑的合成方法，其中发生了前所未有的分子内烯丙基转移，可能涉及五价硅中间体。