(+/-)-2-methyl-5-phenylpent-1-en-3-ol

• 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-methyl-5-phenylpent-1-en-3-ol
• 英文别名: 2-methyl-5-phenyl-1-penten-3-ol；3-hydroxy-2-methyl-5-phenyl-1-pentene；2-methyl-5-phenylpent-1-en-3-ol
• 化学式: C₁₂H₁₆O
• 分子量: 176.258
• InChiKey: SQILPJYCZMADEH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+/-)-2-methyl-5-phenylpent-1-en-3-ol 在 lithium aluminium tetrahydride 、 丙酸 、 三乙胺 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 21.0h， 生成 (E)-4-methyl-7-phenyl-heptan-4-ene-1-ol mesylate
  参考文献：
  名称：

  Tandem carbonyl ene cyclization-cycloalkylation: a route to trifluoromethyl diterpenoids.

  摘要：

  A new sequential carbonyl-ene cyclizatian/cycloalkylation of trifluoromethyl ketones catalyzed by aluminum Lewis acids is described. From ketone 1, the 4-CF3-4-OH cis-octahydrophenanthrene 6 is obtained in 50 % yield. From ketone 2, with MeAlCl(2) a total stereoselective route to the 4-CF3-trans-10-methyl podocarpatrienol 8 (90 % yield) has been found. These studies also exhibited some striking results in the stereochemical outcome of ene cyclizations.

  DOI：

  10.1016/s0040-4020(01)89305-4
• 作为产物：
  描述：

  1-碘-3-苯基丙烷 在 potassium tert-butylate 、 aluminum isopropoxide 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 二氯甲烷 、 甲苯 为溶剂， 反应 40.0h， 生成 (+/-)-2-methyl-5-phenylpent-1-en-3-ol
  参考文献：
  名称：

  Expedient Access to 2,3-Dihydropyridines from Unsaturated Oximes by Rh(III)-Catalyzed C–H Activation

  摘要：

  alpha,beta-Unsaturated - oxime pivalates are proposed to undergo reversible C(sp(2))-H insertion with cationic Rh (III) complexes to furnish five-membered metallacycles. In the presence of 1,1-disubstituted olefins, these species participate in irreversible migratory insertion to give, after reductive elimination, 2,3-dihydropyridine products in good yields. Catalytic hydrogenation can then be used to. convert these molecules into piperidines, which are important structural components of numerous pharmaceuticals.

  DOI：

  10.1021/jacs.5b04946

文献信息

• Highly Regioselective Palladium‐Catalyzed Carboxylation of Allylic Alcohols with CO ₂
  作者：Tsuyoshi Mita、Yuki Higuchi、Yoshihiro Sato

  DOI：10.1002/chem.201503359

  日期：2015.11.9

  stoichiometric transmetalation agent under a CO2 atmosphere (1 atm). This carboxylation proceeded in a highly regioselective manner to afford branched carboxylic acids predominantly. The β,γ‐unsaturated carboxylic acid thus obtained was successfully converted into an optically active γ‐butyrolactone, a known intermediate of (R)‐baclofen.

  使用ZnEt 2作为化学计量的重金属化试剂，在CO 2气氛（1个大气压）下，在催化量的PdCl 2和PPh 3存在下，将各种烯丙醇羧化。该羧化以高度区域选择性的方式进行，主要得到支链羧酸。如此获得的β，γ-不饱和羧酸已成功转化为旋光性γ-丁内酯，这是（R）-baclofen的已知中间体。
• Palladium/Norbornene-Catalyzed <i>ortho</i> Aliphatic Acylation with Mixed Anhydride: Selectivity and Reactivity
  作者：Shibo Xu、Julong Jiang、Linlin Ding、Yao Fu、Zhenhua Gu

  DOI：10.1021/acs.orglett.7b03514

  日期：2018.1.19

  synthesis of functionalized alkyl aryl ketones is reported. Studies on the electronic and steric properties of mixed aryl anhydrides indicated that the cross-coupling favored with the electron-enriched aryl acyl group. DFT calculation on the oxidative addition of Pd(II) with 2,4,6-(Cl)3C6H2CO2C(O)Ph suggested that 2,4,6-(Cl)3C6H2C(O)–O bond cleavage was more kinetically disfavored than that of the PhC(O)–O

  报道了钯/降冰片烯催化的邻位酰化，用于有效合成官能化的烷基芳基酮。对混合的芳基酸酐的电子和空间特性的研究表明，交叉偶联有利于富电子的芳基酰基。用2,4,6-（Cl）3 C 6 H 2 CO 2 C（O）Ph氧化Pd（II）的DFT计算表明2,4,6-（Cl）3 C 6 H 2 C （O）–O键的断裂在动力学上比PhC（O）–O键的断裂更不利于11.7 kJ / mol。
• Electrochemical Nozaki–Hiyama–Kishi Coupling: Scope, Applications, and Mechanism
  作者：Yang Gao、David E. Hill、Wei Hao、Brendon J. McNicholas、Julien C. Vantourout、Ryan G. Hadt、Sarah E. Reisman、Donna G. Blackmond、Phil S. Baran

  DOI：10.1021/jacs.1c03007

  日期：2021.6.30

  practical using an electroreductive manifold. Although early studies pointed to the feasibility of such a process, those precedents were never applied by others due to cumbersome setups and limited scope. Here we show that a carefully optimized electroreductive procedure can enable a more sustainable approach to NHK, even in an asymmetric fashion on highly complex medicinally relevant systems. The e-NHK

  最常用的 C-C 键形成方法之一是使用还原歧管，使卤乙烯与 Ni 和 Cr 催化的醛偶联（Nozaki-Hiyama-Kishi，NHK）变得更加实用。尽管早期研究指出了这种过程的可行性，但由于设置繁琐且范围有限，这些先例从未被其他人应用。在这里，我们展示了经过精心优化的电还原程序可以使 NHK 采用更可持续的方法，即使在高度复杂的医学相关系统上以不对称方式也是如此。当传统化学技术失败时，e-NHK 甚至可以使非规范底物类别（例如氧化还原活性酯）参与低负载量的 Cr。详细的动力学、循环伏安法、
• A Sequential Acyl Thiol–Ene and Thiolactonization Approach for the Synthesis of δ-Thiolactones
  作者：Ruairí O. McCourt、Eoin M. Scanlan

  DOI：10.1021/acs.orglett.9b01271

  日期：2019.5.3

  A novel strategy for the synthesis of δ-thiolactones from inexpensive and readily available γ-unsaturated esters has been developed. This strategy incorporates a radical acyl thiol–ene reaction as the key C–S bond forming step. Cyclization is achieved via a Steglich-type thiolactonization of 5-mercaptopentanoic acids. We report the facile and scalable synthesis of δ-thiolactones in moderate to good

  已开发出一种从廉价且容易获得的γ-不饱和酯合成δ-硫代内酯的新策略。该策略将自由基酰基硫醇-烯反应纳入了关键的CS键形成步骤。通过5-巯基戊酸的Steglicch型硫内酯化来实现环化。我们报道了在温和的反应条件下，对中等官能团具有良好的收率的δ-硫代内酯的简便，可扩展合成，对一系列官能团具有耐受性。
• General, Simple, and Chemoselective Catalysts for the Isomerization of Allylic Alcohols: The Importance of the Halide Ligand
  作者：Elis Erbing、Ana Vázquez-Romero、Antonio Bermejo Gómez、Ana E. Platero-Prats、Fabian Carson、Xiaodong Zou、Päivi Tolstoy、Belén Martín-Matute

  DOI：10.1002/chem.201603825

  日期：2016.10.24

  Remarkably simple IrIII catalysts enable the isomerization of primary and sec‐allylic alcohols under very mild reaction conditions. X‐ray absorption spectroscopy (XAS) and mass spectrometry (MS) studies indicate that the catalysts, with the general formula [Cp*IrIII], require a halide ligand for catalytic activity, but no additives or additional ligands are needed.

  非常简单的Ir III催化剂可在非常温和的反应条件下实现伯醇和仲烯丙基醇的异构化。X射线吸收光谱（XAS）和质谱（MS）研究表明，通式为[Cp * Ir III ]的催化剂需要卤化物配体才能发挥催化活性，但不需要添加剂或其他配体。