(R)-1-(4-hydroxyphenyl)propanol

• 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: (R)-1-(4-hydroxyphenyl)propanol
• 英文别名: 4-(1-hydroxyprop-1-yl)phenol；(S)-4-(1-hydroxypropyl)phenol；4-[(1S)-1-hydroxypropyl]phenol
• 化学式: C₉H₁₂O₂
• 分子量: 152.193
• InChiKey: WEKMUBUZJDWJIR-VIFPVBQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  4-羟基苯丙酮 在 bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 氢气 、 C₄₅H₃₈FeNO₂P 、 sodium hydroxide 作用下， 以 乙醇 为溶剂， 25.0~30.0 ℃ 、2.03 MPa 条件下， 以99 %的产率得到(R)-1-(4-hydroxyphenyl)propanol
  参考文献：
  名称：

  具有 f-两性醇配体的铱催化剂：各种酮的高度立体选择性氢化

  摘要：

  成功合成了一系列新型模块化二价铁基氨基膦二醇（f-两性醇）配体。 f-两性醇配体在 Ir 催化的各种酮的立体选择性氢化中表现出极高的空气稳定性和催化效率，得到相应的立体定义的醇，并具有优异的结果（完全转化，顺式/反式 >99:1，和 83% → 99% ee） ，TON 高达 500 000）。对照实验表明-OH和-NH基团在这种立体选择性氢化中发挥了关键作用。

  DOI：

  10.1021/acs.orglett.3c03550

文献信息

• The reaction mechanism of chiral hydroxylation of <i>p</i>-OH and <i>p</i>-NH₂ substituted compounds by ethylbenzene dehydrogenase
  作者：Agnieszka Dudzik、Bartłomiej Kozik、Mateusz Tataruch、Anna Wójcik、Daniel Knack、Tomasz Borowski、Johann Heider、Małgorzata Witko、Maciej Szaleniec

  DOI：10.1139/cjc-2012-0504

  日期：2013.9

  Ethylbenzene dehydrogenase (EbDH; enzyme commission (EC) number: 1.17.99.2) is a unique biocatalyst that hydroxylates alkylaromatic and alkylheterocyclic compounds to (S)-secondary alcohols under anaerobic conditions. The enzyme exhibits a high promiscuity catalyzing oxidation of over 30 substrates, inter alia, para-substituted alkylphenols and alkylanilines. Secondary alcohols with OH and NH₂ substituents in the aromatic ring are highly valuable synthons for many biologically active compounds in the fine chemical industry. EbDH hydroxylates most of the studied compounds highly enantioselectively, except for five substrates that harbour OH and NH₂ groups in the para position, which exhibit a significant decrease in the percent enantiomeric excess (% ee). This phenomenon is inconsistent with the previously suggested enzyme mechanism, but it may be linked to a stabilization of the carbocation intermediate by deprotonation of the OH or NH₂ substituent in the active site that yields a transient quinone (imine) ethide species. This would initiate an alternative reaction pathway involving the addition of a water molecule to a C=C double bond. This hypothesis was cross-validated by density functional theory (DFT) cluster modelling of the alternative reaction pathway with 4-ethylphenol, as well as by experimental assessment of the pH dependency of enantiomeric excesses. The results reported herein suggest that the alternative reaction pathway may significantly contribute to the overall reaction if the carbocation intermediates are stabilized by deprotonation.

  乙苯脱氢酶（EbDH；酶学委员会（EC）编号：1.17.99.2）是一种独特的生物催化剂，在厌氧条件下将烷基芳香化合物和烷基杂环化合物羟基化为（S）-次生醇。该酶表现出很高的催化广谱性，催化氧化超过30种底物，包括对位取代的烷基酚和烷基苯胺。具有芳香环中OH和NH₂取代基的次生醇对于精细化工行业中许多生物活性化合物是非常有价值的合成物。EbDH在高对映选择性地羟基化大多数研究过的化合物，除了五种在对位位置带有OH和NH₂基团的底物，其对映异构体过量百分比（% ee）显著降低。这种现象与先前提出的酶机制不一致，但可能与在活性位点上通过去质子化OH或NH₂取代基稳定卡宾中间体有关，从而产生瞬时的醌（亚胺）乙烯基物种。这将启动涉及将水分子加到C=C双键的另一反应途径。通过密度泛函理论（DFT）对4-乙基酚的替代反应途径进行了簇模拟，以及通过对对映异构体过量的pH依赖性的实验评估，交叉验证了这一假设。本文报道的结果表明，如果通过去质子化稳定卡宾中间体，则替代反应途径可能会显著影响整体反应。
• METHOD AND COMPOSITIONS FOR BIOFOULING DETERRENCE
  申请人：Mount Andrew S.

  公开号：US20110123477A1

  公开（公告）日：2011-05-26

  A method of deterring biofouling of a surface comprising attaching an adduct having formula (I) or noradrenalin to the surface. Formula (I) being defined as compounds that have the formula A-L-R wherein A is i) a C6 or C10 substituted aryl ring, or ii) a C1-C9 substituted or unsubstituted heteroaryl ring: L is a linking group, and R is a primary amino moiety comprising unit.

  一种防止生物污垢的方法，包括将具有公式（I）或去甲肾上腺素的加合物附着到表面上。公式（I）被定义为具有公式A-L-R的化合物，其中A是i）C6或C10取代的芳基环，或ii）C1-C9取代或未取代的杂环；L是连接基团，R是包含单元的一级氨基团。
• Synthesis of (S)-1-(4-hydroxyphenyl)alcohols by eugenol dehydrogenase from Pseudomonas fluorescens E118
  作者：Marco Wieser、Hirotaka Furukawa、Hiroshi Morita、Toyokazu Yoshida、Toru Nagasawa

  DOI：10.1016/s0957-4166(99)00164-0

  日期：1999.5

  (S)-1-(4-Hydroxyphenyl)ethanol and (S)-1-(4-hydroxyphenyl)propanol were synthesized with enantiomeric excesses of 96.6% and 95.2%, respectively, from the corresponding 4-alkylphenols by eugenol dehydrogenase from Pseudomonas fluorescens E118. The enantioselectivity of the enzyme was shown to be pH-dependent. (C) 1999 Elsevier Science Ltd. All rights reserved.
• US9560848B2
  申请人：——

  公开号：US9560848B2

  公开（公告）日：2017-02-07
• Iridium Catalysts with f-Amphbinol Ligands: Highly Stereoselective Hydrogenation of a Variety of Ketones
  作者：Weilong Wu、Niu Zhao、Yiyi Liu、Shenshen Du、Xinxin Wang、Wenzhi Mo、Xianghe Yan、Chunying Xu、Yan Zhou、Baoming Ji

  DOI：10.1021/acs.orglett.3c03550

  日期：2023.12.15

  catalytic efficiency in the Ir-catalyzed stereoselective hydrogenation of various ketones to afford corresponding stereodefined alcohols with excellent results (full conversions, cis/trans >99:1, and 83% → 99% ee, TON up to 500 000). Control experiments have shown that −OH and −NH groups played a key role in this stereoselective hydrogenation.

  成功合成了一系列新型模块化二价铁基氨基膦二醇（f-两性醇）配体。 f-两性醇配体在 Ir 催化的各种酮的立体选择性氢化中表现出极高的空气稳定性和催化效率，得到相应的立体定义的醇，并具有优异的结果（完全转化，顺式/反式 >99:1，和 83% → 99% ee） ，TON 高达 500 000）。对照实验表明-OH和-NH基团在这种立体选择性氢化中发挥了关键作用。