[18O]-1-phenylethanol | 73020-77-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: [18O]-1-phenylethanol
• 英文别名: <18O>-1-phenyl-1-ethanol；[¹⁸O]-1-phenylethanol；1-phenylethanol-¹⁸O
• CAS: 73020-77-6
• 化学式: C₈H₁₀O
• 分子量: 124.167
• InChiKey: WAPNOHKVXSQRPX-FOQJRBATSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.74
• 重原子数：
  9.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  [18O]-1-phenylethanol 生成 <18O>-(R)-1-phenyl-1-ethanol
  参考文献：
  名称：

  Enantiomer-Specific Oxygen Exchange Reactions. 2. Acid-Catalyzed Water Exchange with 1-Phenyl-1-alkanols

  摘要：

  The rate constants for three competing processes at the chiral center in the acid-catalyzed racemization of (R)-1-phenyl-1-propanol and (R)-1-phenyl-1-butanol at 64.5 +/- 1.0 OC have been determined by chiral HPLC and GC/MS methods: oxygen exchange without inversion, k(E), oxygen exchange with inversion, k(EI), and inversion without exchange, k(I). These same rate constants, previously determined for natural abundance 1-phenylethanol in 50% O-18-enriched water, have been reevaluated for this compound by following the kinetics of 91% O-18-enriched alcohol in natural abundance water. These latter data strengthen the evidence that, for 1-phenylethanol, the departing water, in some cases, bonds to the opposite face of the intermediate carbocation as indicated by a non-zero value for k(I); this process is also operative in the reactions of the other two alkanols as shown by similar kinetic data. In terms of substitution reactions with the solvent leading to oxygen exchange, phenylpropanol behaves similarly to phenylethanol in that k(E) < k(EI); whereas, for phenylbutanol, k(E) approximate to K-EI. A common mechanism in which the initially formed carbocation is present as a complex with the departing water, an ion-molecule pair, can account for the variations in the relative rate constants for the oxygen exchange reactions of these three alcohols. The rate of motion of water molecules within the solvation sphere of these intermediates relative to their exchange with the bulk solvent to form randomly solvated carbocations differs, depending on the substituent at the chiral center. The variations in the rate constants for the oxygen exchange reactions reflect these differences in water mobility.

  DOI：

  10.1021/ja00092a005
• 作为产物：
  描述：

  苏合香醇 在 高氯酸 、 重氧水 作用下， 生成 [18O]-1-phenylethanol
  参考文献：
  名称：

  Enantiomer-Specific Oxygen Exchange Reactions. 2. Acid-Catalyzed Water Exchange with 1-Phenyl-1-alkanols

  摘要：

  The rate constants for three competing processes at the chiral center in the acid-catalyzed racemization of (R)-1-phenyl-1-propanol and (R)-1-phenyl-1-butanol at 64.5 +/- 1.0 OC have been determined by chiral HPLC and GC/MS methods: oxygen exchange without inversion, k(E), oxygen exchange with inversion, k(EI), and inversion without exchange, k(I). These same rate constants, previously determined for natural abundance 1-phenylethanol in 50% O-18-enriched water, have been reevaluated for this compound by following the kinetics of 91% O-18-enriched alcohol in natural abundance water. These latter data strengthen the evidence that, for 1-phenylethanol, the departing water, in some cases, bonds to the opposite face of the intermediate carbocation as indicated by a non-zero value for k(I); this process is also operative in the reactions of the other two alkanols as shown by similar kinetic data. In terms of substitution reactions with the solvent leading to oxygen exchange, phenylpropanol behaves similarly to phenylethanol in that k(E) < k(EI); whereas, for phenylbutanol, k(E) approximate to K-EI. A common mechanism in which the initially formed carbocation is present as a complex with the departing water, an ion-molecule pair, can account for the variations in the relative rate constants for the oxygen exchange reactions of these three alcohols. The rate of motion of water molecules within the solvation sphere of these intermediates relative to their exchange with the bulk solvent to form randomly solvated carbocations differs, depending on the substituent at the chiral center. The variations in the rate constants for the oxygen exchange reactions reflect these differences in water mobility.

  DOI：

  10.1021/ja00092a005

文献信息

• Reactivity of an Iron–Oxygen Oxidant Generated upon Oxidative Decarboxylation of Biomimetic Iron(II) α-Hydroxy Acid Complexes
  作者：Sayantan Paria、Sayanti Chatterjee、Tapan Kanti Paine

  DOI：10.1021/ic402443r

  日期：2014.3.17

  study the mechanism of dioxygen activation at the iron(II) centers. Single-crystal X-ray structural analyses of 1, 2, and 5 were performed to assess the binding mode of an α-hydroxy/methoxy acid anion to the iron(II) center. While the iron(II) α-methoxy acid complexes are unreactive toward dioxygen, the iron(II) α-hydroxy acid complexes undergo oxidative decarboxylation, implying the importance of the

  三种仿生铁（II）α-羟基酸络合物[[Tp Ph2）Fe II（扁桃酸盐）（H 2 O）]（1），[（Tp Ph2）Fe II（苯甲酸盐）]（2）和[（ Tp Ph2）Fe II（HMP）]（3）以及两个铁（II）α-甲氧基酸络合物[[（Tp Ph2）Fe II（MPA）]（4）和[（Tp Ph2）Fe II（MMP） ）]（5）（其中HMP = 2-羟基-2-甲基丙酸酯，MPA = 2-甲氧基-2-苯基乙酸酯，MMP = 2-甲氧基-2-甲基丙酸酯），面部三齿配体Tp Ph2分离[其中Tp Ph2 =氢三（3,5-二苯基吡唑-1-基）硼酸酯]并进行表征，以研究铁（II）中心的双氧活化机理。的单晶X射线结构分析1，2，和5进行，以评估一个α羟基/酸甲氧基阴离子的铁（II）中心的结合模式。尽管铁（II）α-甲氧基酸络合物对双氧不反应，但铁（II）α-羟基酸络合物进行氧化脱羧，这暗示了羟基在双
• Mechanistic elucidation of C–H oxidation by electron rich non-heme iron(<scp>iv</scp>)–oxo at room temperature
  作者：Sujoy Rana、Aniruddha Dey、Debabrata Maiti

  DOI：10.1039/c5cc04803f

  日期：——

  Non-heme iron(iv)–oxo species form iron(iii) intermediates during hydrogen atom abstraction (HAA) from the C–H bond.

  非血红素铁（IV）-氧物种在从C-H键中进行氢原子提取（HAA）过程中形成铁（III）中间体。
• Pd-Catalyzed Aerobic Oxidation Reactions: Strategies To Increase Catalyst Lifetimes
  作者：Wilson C. Ho、Kevin Chung、Andrew J. Ingram、Robert M. Waymouth

  DOI：10.1021/jacs.7b11372

  日期：2018.1.17

  10-phenanthroline) is an effective catalyst precursor for the selective oxidation of primary and secondary alcohols, vicinal diols, polyols, and carbohydrates. Both air and benzoquinone can be used as terminal oxidants, but aerobic oxidations are accompanied by oxidative degradation of the neocuproine ligand, thus necessitating high Pd loadings. Several strategies to improve aerobic catalyst lifetimes were devised

  钯络合物 [(neocuproine)Pd(μ-OAc)]2[OTf]2 (1, neocuproine = 2,9-dimethyl-1,10-phenanthroline) 是伯醇和仲醇选择性氧化的有效催化剂前体、邻二醇、多元醇和碳水化合物。空气和苯醌都可以用作末端氧化剂，但有氧氧化伴随着新铜碱配体的氧化降解，因此需要高 Pd 负载。在催化剂失活的机理研究的指导下，设计了几种提高有氧催化剂寿命的策略。这些研究暗示了从新铜碱配体中提取 H 原子引发的自由基自氧化机制。旨在延缓 H 原子提取以及添加牺牲性 H 原子供体的配体修饰增加了催化剂寿命并导致在有氧条件下更高的周转数 (TON)。其他研究表明，添加苄型氢过氧化物或苯乙烯也会导致 TON 显着增加。机理研究表明，苄型氢过氧化物充当 H 原子供体，而苯乙烯可有效拦截 Pd 氢化物。这些策略能够使用低至 0.25 mol% 的 Pd 以制
• Selective C–H halogenation over hydroxylation by non-heme iron(<scp>iv</scp>)-oxo
  作者：Sujoy Rana、Jyoti Prasad Biswas、Asmita Sen、Martin Clémancey、Geneviève Blondin、Jean-Marc Latour、Gopalan Rajaraman、Debabrata Maiti

  DOI：10.1039/c8sc02053a

  日期：——

  iron(IV)-oxo complex, [Fe(2PyN2Q)(O)]2+ was directed for hydrogen atom abstraction (HAA) from aliphatic substrates and the iron(II)-halide [FeII(2PyN2Q)(X)]+ (X, halogen) was exploited in conjunction to deliver the halogen atom to the ensuing carbon centered radical. Despite iron(IV)-oxo being an effective promoter of hydroxylation of aliphatic substrates, the perfect interplay of HAA and halogen atom

  非血红素铁基卤化酶通过铁 ( IV )-氧代卤化物活性物质促进 sp 3 -C–H 键的选择性卤化。在卤化过程中，酶系统中可以完全防止竞争性羟基化。然而，合成铁( IV )-氧代-卤化物中间体通常会产生卤化和羟基化产物的混合物。在本报告中，我们开发了一种新的合成策略，采用非血红素铁基配合物通过超越羟基化进行选择性 sp 3 -C–H 卤化。室温稳定的铁( IV )-氧配合物 [Fe(2PyN2Q)(O)] 2+用于从脂肪族底物和铁( II )-卤化物 [Fe II (2PyN2Q) 中夺取氢原子 (HAA) (X)] + (X，卤素) 结合使用将卤素原子传递给随后的碳中心基团。尽管铁( IV )-氧代是脂肪族底物羟基化的有效促进剂，但本研究中HAA和卤素原子转移的完美相互作用导致通过改变羟基化途径选择性地产生卤化产物。实验研究概述了铁( IV )-氧介导的卤化反应的机制细节。PhCH 3和
• Unprecedented Reactivities of Highly Reactive Manganese(III)–Iodosylarene Porphyrins in Oxidation Reactions
  作者：Lina Zhang、Yong-Min Lee、Mian Guo、Shunichi Fukuzumi、Wonwoo Nam

  DOI：10.1021/jacs.0c10159

  日期：2020.11.25

  behavior of reaction rates and no electronic effect of porphyrin ligands on reactivities. The reactivities and mechanisms of [MnIII(Porp)(sArIO)]+ are then compared with those of the corresponding MnIV(Porp)(O) complex. The present study reports the first example of highly reactive Mn(III)-iodosylarene porphyrins with unprecedented reactivities in C-H bond activation and OAT reactions.

  我们报告说，Mn(III)-碘代芳烃卟啉 [MnIII(Porp)(sArIO)]+ 能够激活烃的 CH 键，包括未活化的烷烃，如环己烷，具有前所未有的反应性，如低动力学同位素效应，反应速率的饱和行为，并且卟啉配体对 [MnIII(Porp)(sArIO)]+ 的反应性没有电子效应。在氧原子转移 (OAT) 反应中，[MnIII(Porp)(sArIO)]+ 对对位 X 取代的苯硫醚的亚砜化在哈米特图中提供了一种非常不寻常的行为，具有反应速率的饱和行为并且没有电子效应卟啉配体对反应的影响。然后将 [MnIII(Porp)(sArIO)]+ 的反应性和机制与相应的 MnIV(Porp)(O) 复合物进行比较。