(-)-1-(4-methoxy-phenyl)-pentan-1-ol | 1005347-89-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (-)-1-(4-methoxy-phenyl)-pentan-1-ol
• 英文别名: (-)-(S)-1-(4-methoxyphenyl)pentan-1-ol；(1S)-1-(4-methoxyphenyl)pentan-1-ol
• CAS: 1005347-89-6
• 化学式: C₁₂H₁₈O₂
• 分子量: 194.274
• InChiKey: KVFBEMVPJGNXSD-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  甲氧基-三氟甲基苯 、 (-)-1-(4-methoxy-phenyl)-pentan-1-ol 在 4-二甲氨基吡啶 作用下， 以 氯仿 为溶剂， 反应 0.5h， 生成 (R)-3,3,3-Trifluoro-2-methoxy-2-phenyl-propionic acid (S)-1-(4-methoxy-phenyl)-pentyl ester
  参考文献：
  名称：

  Ti-TADDOLate-catalyzed, highly enantioselective addition of alkyl- and aryl-titanum derivatives to aldehydes

  摘要：

  Toluene-ether or toluene-hexane solutions of aryl and alkyl triisopropoxy titanium reagents (free of Li, Mg, or Zn salts) are prepared from the corresponding Li or Grignard reagents and ClTi((OPr)-Pr-i)(3), with careful removal of salts (centrifugation of LiCl or of dioxane.MgX(2), and addition of 12-crown-4). The solutions of the organotitanium compounds are combined with one equiv. of an aldehyde and 0.2 equiv. of (R,R)-diisopropoxy-(alpha,alpha,alpha',alpha'-tetraphenyl-2,2-dimethyl-1,3-dioxolane-4,5-dimethanolato) titanium (Ti-TADDOLate 3) at dry-ice temperature. Warming up to room temperature leads to nucleophilic addition to the (Si)-face of the aldehydes with enantioselectivities as high as 99.5 : 0.5 (products 4 - 33 in Scheme 4). Functional groups or protecting groups and branching in the Ti-R group and in the aldehyde must be remote from the reacting centers. Aryl groups can be added to aldehydes by this method. - In contrast to all the enantioselective R(2)Zn additions to aldehydes, in which only one R-group is actually transferred, a twice as economic use is made of the originally employed R-metal reagent in the method described here. - A procedure for multigram preparation of the spiro-Ti-TADDOLate (2) employed for the in situ generation of the catalyst (3) is described, and details of the determination of enantiomer ratios (er) by GC and NMR methods are given (Tab. 2, 3). The mechanistic interpretation of Ti-TADDOLate-mediated nucleophilic additions as derived previously (ref.(4e)) is also compatible with this monometallic variant of the method.

  DOI：

  10.1016/s0040-4020(01)90475-2
• 作为产物：
  描述：

  dibutyl-[(1S)-1-(4-methoxyphenyl)pentyl]borane 在 sodium hydroxide 、 双氧水 作用下， 以 甲苯 为溶剂， 反应 16.0h， 生成 (-)-1-(4-methoxy-phenyl)-pentan-1-ol
  参考文献：
  名称：

  胺的不对称锂取代反应涉及硼酸酯的重排。

  摘要：

  使用Beak方法对取代的苄胺，N-Boc-吡咯烷或N-Boc-二氢吲哚进行不对称锂化反应，然后用三烷基硼烷进行亲电淬灭。所得的硼酸盐中间体重排，同时CN键断裂，从而在氧化后得到具有高对映选择性的手性仲醇。

  DOI：

  10.1021/ol702734u

文献信息

• Catalytic Asymmetric Addition of Alkyllithium Reagents to Aromatic Aldehydes
  作者：Emilio Fernández-Mateos、Beatriz Maciá、Miguel Yus

  DOI：10.1002/ejoc.201200464

  日期：2012.7

  Herein, we report the first efficient catalytic system for the asymmetric alkylation of aldehydes with organolithium reagents in the presence of titanium(IV) isopropoxide. A variety of alkyllithium reagents can be added to aromatic aldehydes in good yields with high enantioselectivities in a simple one-pot procedure under mild conditions.

  在此，我们报告了第一个在异丙醇钛 (IV) 存在下用有机锂试剂对醛进行不对称烷基化的有效催化体系。在温和的条件下，通过简单的一锅程序，可以将各种烷基锂试剂以良好的收率和高对映选择性添加到芳族醛中。
• Catalytic Enantioselective Addition of MeMgBr and Other Grignard Reagents to Aldehydes
  作者：Emilio Fernández-Mateos、Beatriz Maciá、Diego J. Ramón、Miguel Yus

  DOI：10.1002/ejoc.201101283

  日期：2011.12

  Herein, we report an efficient catalyst for the challenging enantioselective addition of MeMgBr to aldehydes. Unprecedented yields and enantioselectivities are achieved in the reaction with a broad range of aldehydes. Moreover, a variety of Grignard reagents can be also added to aromatic and aliphatic aldehydes in good yields and enantioselectivities in a simple one-pot procedure under mild conditions.

  在这里，我们报告了一种有效的催化剂，用于将 MeMgBr 具有挑战性的对映选择性加成到醛中。在与多种醛的反应中实现了前所未有的产率和对映选择性。此外，还可以在温和条件下通过简单的一锅程序将各种格氏试剂以良好的收率和对映选择性添加到芳香族和脂肪族醛中。
• On the Scope of Trimethylaluminium-Promoted 1,2-Additions of ArZnX Reagents to Aldehydes
  作者：Daniel Glynn、Jonathan Shannon、Simon Woodward

  DOI：10.1002/chem.200901803

  日期：2010.1.18

  functionalised arylzinc halides to aromatic and aliphatic aldehydes is described by the use of aminoalcohol catalysis in the presence of AlMe3. The process is simple to carry out, uses only commercially available reagents/ligands and provides moderate to good (80–96 % ee) enantioselectivities for a wide range of substrates. Either commercial ArZnX reagents or those prepared in situ from low cost aryl bromides

  通过在AlMe 3存在下使用氨基醇催化，描述了官能化的芳基卤化锌与芳族和脂族醛的不对称1,2-加成反应。该方法操作简单，仅使用市售试剂/配体，并能为多种底物提供中等至良好（80-96％ee）的对映选择性。可以使用市售的ArZnX试剂，也可以使用由低成本的芳基溴化物原位制备的试剂。在后一种情况下，可以耐受亲电官能团（CO 2 Et，CN）。该反应依赖于ArZnX和AlMe 3之间的快速交换，生成混合的有机金属物质，从而导致形成与经典“Noyori的“反”过渡状态。核磁共振监测和相关实验已被用来探测所提出的选择性过渡态的有效性。
• Ti-TADDOLate-catalyzed, highly enantioselective addition of alkyl- and aryl-titanum derivatives to aldehydes
  作者：Beat Weber、Dieter Seebach

  DOI：10.1016/s0040-4020(01)90475-2

  日期：——

  Toluene-ether or toluene-hexane solutions of aryl and alkyl triisopropoxy titanium reagents (free of Li, Mg, or Zn salts) are prepared from the corresponding Li or Grignard reagents and ClTi((OPr)-Pr-i)(3), with careful removal of salts (centrifugation of LiCl or of dioxane.MgX(2), and addition of 12-crown-4). The solutions of the organotitanium compounds are combined with one equiv. of an aldehyde and 0.2 equiv. of (R,R)-diisopropoxy-(alpha,alpha,alpha',alpha'-tetraphenyl-2,2-dimethyl-1,3-dioxolane-4,5-dimethanolato) titanium (Ti-TADDOLate 3) at dry-ice temperature. Warming up to room temperature leads to nucleophilic addition to the (Si)-face of the aldehydes with enantioselectivities as high as 99.5 : 0.5 (products 4 - 33 in Scheme 4). Functional groups or protecting groups and branching in the Ti-R group and in the aldehyde must be remote from the reacting centers. Aryl groups can be added to aldehydes by this method. - In contrast to all the enantioselective R(2)Zn additions to aldehydes, in which only one R-group is actually transferred, a twice as economic use is made of the originally employed R-metal reagent in the method described here. - A procedure for multigram preparation of the spiro-Ti-TADDOLate (2) employed for the in situ generation of the catalyst (3) is described, and details of the determination of enantiomer ratios (er) by GC and NMR methods are given (Tab. 2, 3). The mechanistic interpretation of Ti-TADDOLate-mediated nucleophilic additions as derived previously (ref.(4e)) is also compatible with this monometallic variant of the method.
• Asymmetric Lithiation−Substitution of Amines Involving Rearrangement of Borates
  作者：Iain Coldham、Jignesh J. Patel、Sophie Raimbault、David T. E. Whittaker、Harry Adams、Guang Y. Fang、Varinder K. Aggarwal

  DOI：10.1021/ol702734u

  日期：2008.1.1

  Asymmetric lithiation of substituted benzylamines, N-Boc-pyrrolidine, or N-Boc-indoline using Beak's methodology was followed by electrophilic quench with trialkylboranes. The resulting borate intermediates rearrange with concomitant C-N bond breakage to give, after oxidation, chiral secondary alcohols with high enantioselectivity.

  使用Beak方法对取代的苄胺，N-Boc-吡咯烷或N-Boc-二氢吲哚进行不对称锂化反应，然后用三烷基硼烷进行亲电淬灭。所得的硼酸盐中间体重排，同时CN键断裂，从而在氧化后得到具有高对映选择性的手性仲醇。