4-phenylbenzyl alcohol-d₁h₁ | 344886-20-0

• 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: 4-phenylbenzyl alcohol-d₁h₁
• 英文别名: α-d-4-biphenylmethanol；Deuterio-(4-phenylphenyl)methanol
• CAS: 344886-20-0
• 化学式: C₁₃H₁₂O
• 分子量: 185.23
• InChiKey: AXCHZLOJGKSWLV-MMIHMFRQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 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：

  4-phenylbenzyl alcohol-d₁h₁ 在 氯化亚砜 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以57%的产率得到4-phenylbenzyl chloride-d₁h₁
  参考文献：
  名称：

  Pd(OAc)2/4,5-Diazafluoren-9-one催化需氧烯丙基C-H乙酰氧基化的操作光谱和动力学表征

  摘要：

  烯丙基 CH 乙酰氧基化是研究最广泛的钯 (II) 催化 CH 氧化反应之一。虽然主要反应步骤已经确立，但催化机制的关键特征却没有得到很好的表征，包括周转限制步骤和催化剂静止状态的特性。在这里，我们报告了使用由 Pd(OAc)2 和 4,5-二氮杂芴-9-one (DAF) 组成的催化剂体系对烯丙基苯进行有氧烯丙基乙酰氧基化的机理研究。DAF 配体的独特之处在于其支持有氧催化转化的能力，即使在没有苯醌或其他助催化剂的情况下也是如此。在此，我们描述了使用 X 射线吸收和 NMR 光谱方法对催化反应进行的操作光谱分析，这些方法允许直接观察反应过程中钯 (I) 物种的形成和衰变。动力学研究表明存在两个不同的动力学阶段：(1) 爆发阶段，包括快速形成烯丙基乙酰氧基化产物和形成二聚 PdI 复合物 [PdI(DAF)(OAc)]2，然后是 (2)爆发后阶段与催化剂静止状态从 PdI 二聚体演变为 π-烯丙基-PdII

  DOI：

  10.1021/jacs.9b04699
• 作为产物：
  描述：

  对苯基苯甲醛 在 lithium aluminium deuteride 作用下， 以 四氢呋喃 为溶剂， 以85%的产率得到4-phenylbenzyl alcohol-d₁h₁
  参考文献：
  名称：

  Pd(OAc)2/4,5-Diazafluoren-9-one催化需氧烯丙基C-H乙酰氧基化的操作光谱和动力学表征

  摘要：

  烯丙基 CH 乙酰氧基化是研究最广泛的钯 (II) 催化 CH 氧化反应之一。虽然主要反应步骤已经确立，但催化机制的关键特征却没有得到很好的表征，包括周转限制步骤和催化剂静止状态的特性。在这里，我们报告了使用由 Pd(OAc)2 和 4,5-二氮杂芴-9-one (DAF) 组成的催化剂体系对烯丙基苯进行有氧烯丙基乙酰氧基化的机理研究。DAF 配体的独特之处在于其支持有氧催化转化的能力，即使在没有苯醌或其他助催化剂的情况下也是如此。在此，我们描述了使用 X 射线吸收和 NMR 光谱方法对催化反应进行的操作光谱分析，这些方法允许直接观察反应过程中钯 (I) 物种的形成和衰变。动力学研究表明存在两个不同的动力学阶段：(1) 爆发阶段，包括快速形成烯丙基乙酰氧基化产物和形成二聚 PdI 复合物 [PdI(DAF)(OAc)]2，然后是 (2)爆发后阶段与催化剂静止状态从 PdI 二聚体演变为 π-烯丙基-PdII

  DOI：

  10.1021/jacs.9b04699

文献信息

• Selective oxidation of alcohol-<i>d</i>₁ to aldehyde-<i>d</i>₁ using MnO₂
  作者：Hironori Okamura、Yoko Yasuno、Atsushi Nakayama、Katsushi Kumadaki、Kohei Kitsuwa、Keita Ozawa、Yusaku Tamura、Yuki Yamamoto、Tetsuro Shinada

  DOI：10.1039/d1ra05405h

  日期：——

  The selective oxidation of alcohol-d1 to prepare aldehyde-d1 was newly developed by means of NaBD4 reduction/activated MnO2 oxidation. Various aldehyde-d1 derivatives including aromatic and unsaturated aldehyde-d1 can be prepared with a high deuterium incorporation ratio (up to 98% D). Halogens (chloride, bromide, and iodide), alkene, alkyne, ester, nitro, and cyano groups in the substrates are tolerated

  醇-d 1的选择性氧化制备醛-d 1是通过NaBD 4还原/活化的MnO 2氧化的新方法。各种醛-d 1衍生物，包括芳族和不饱和醛-d 1都可以以高氘掺入率（高达 98% D）制备。在温和条件下，底物中的卤素（氯化物、溴化物和碘化物）、烯烃、炔烃、酯、硝基和氰基是可耐受的。
• Photocatalytic Carbinol Cation/Anion Umpolung: Direct Addition of Aromatic Aldehydes and Ketones to Carbon Dioxide
  作者：Shintaro Okumura、Yasuhiro Uozumi

  DOI：10.1021/acs.orglett.1c02592

  日期：2021.9.17

  We have developed a new photocatalytic umpolung reaction of carbonyl compounds to generate anionic carbinol synthons. Aromatic aldehydes or ketones reacted with carbon dioxide in the presence of an iridium photocatalyst and 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzimidazole (DMBI) as a reductant under visible-light irradiation to furnish the corresponding α-hydroxycarboxylic acids through nucleophilic

  我们开发了一种新的羰基化合物光催化聚合反应，以生成阴离子甲醇合成子。芳香醛或酮在铱光催化剂和 1,3-二甲基-2-苯基-2,3-二氢-1 H-苯并咪唑 (DMBI) 作为还原剂的存在下与二氧化碳反应，在可见光照射下提供通过将所得的甲醇阴离子与亲电二氧化碳进行亲核加成，生成相应的α-羟基羧酸。
• Photocatalytic Cross‐Pinacol Coupling Promoted by Carbon Dioxide**
  作者：Shintaro Okumura、Teruki Takahashi、Kaoru Torii、Yasuhiro Uozumi

  DOI：10.1002/chem.202300840

  日期：2023.8.4

  A first photocatalytic cross-pinacol coupling was achieved. The reaction proceeded with a various combination of two aldehydes, two ketones, or an aldehyde and a ketone to afford the corresponding unsymmetric vicinal 1,2-diols in up to 91 % yield. In this process, an umpoled anionic carbinol synthon was generated in situ, by the assistance of CO2 additive, to react nucleophilically with a second electrophilic

  首次实现了光催化交叉频哪醇偶联。该反应以两种醛、两种酮或醛和酮的各种组合进行，以高达 91% 的产率提供相应的不对称邻位 1,2-二醇。在此过程中，在 CO 2添加剂的帮助下，原位生成了反极性的阴离子甲醇合成子，与第二个亲电子羰基化合物发生亲核反应。二氧化碳促进的光催化交叉频哪醇偶联（S. Okumura、Y. Uozumi 等）等）
• Umpolung of a Hydrogen Atom of Water by Using a Hexacoordinated Phosphate and Its Application to Deuteride Reduction Reactions of Carbonyl Compounds
  作者：Hideaki Miyake、Naokazu Kano、Takayuki Kawashima

  DOI：10.1021/ja906875d

  日期：2009.11.25

  The polarity of a chemical bond is an important factor that determines the reactivity because a reaction of a positively charged atom with a negatively charged atom easily occurs. We report here a method for reversing the polarity of a hydrogen atom of water, which meant conversion of a protic hydrogen (H(delta+)) to a hydridic hydrogen (H(delta-)), by using a hexacoordinated phosphorus species. The method enables a reductive deuteration of carbonyl compounds utilizing inexpensive and easily usable D2O under mild conditions. The umpolung of a hydrogen atom was achieved by utilizing tautomerization of phosphorus compounds. Classical metal hydrides never have this function, and these results demonstrated the potential utility of nonmetallic compounds for umpolung of a hydrogen atom.
• Isolation of a Metastable Geometrical Isomer of a Hexacoordinated Dihydrophosphate: Elucidation of Its Enhanced Reactivity in Umpolung of a Hydrogen Atom of Water
  作者：Hideaki Miyake、Naokazu Kano、Takayuki Kawashima

  DOI：10.1021/ic2012765

  日期：2011.9.19

  Two of five conceivable geometrical isomers of a hexacoordinated dihydrophosphate bearing two sets of a bidentate ligand were investigated. X-ray crystallographic analysis of both of isomers, 1a-TPP and 1b-TEA, revealed their octahedral geometries of C-2 and C-1 symmetry, respectively, which were consistent with the NMR spectra. The isomer 1b-TEA underwent both hydride reduction of an aldehyde and proton exchange with water at room temperature in DMSO without any additive. A one-pot reaction of both of the reactions of 1b-TEA with D2O and an aldehyde or a ketone under the above conditions proceeded successfully to give the deuterated alcohol. Thus, umpolung of a hydrogen atom of water with 1b-TEA was achieved under much milder conditions than those used in the reaction with another isomer, la-TEA. Quantitative isomerization of 1b-TEA to la-TEA occurred in methanol at room temperature. Calculations on the five conceivable geometrical isomers of the anionic part of the dihydrophosphate revealed their relative stability, which reasonably explained the isomerization, and the larger negative charge at the atoms located at the trans positions of the oxygen atoms. The smaller coupling constants of the P H and P C bonds located at the rear of an oxygen atom in the NMR spectra resulted in the smaller s character of these bonds. The differences in both hydride-donation and proton-exchange reactivities between la-TEA and 1b-TEA could be explained by the differences in the atomic charge of the hydrogen atom and the stability difference of the initially formed phosphorane intermediates, respectively.