o-Nitrozimtalkohol | 1504-65-0

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂醇
• 英文名称: o-Nitrozimtalkohol
• 英文别名: 3-(2-nitrophenyl)prop-2-en-1-ol；2-nitrocinnamyl alcohol
• CAS: 1504-65-0
• 化学式: C₉H₉NO₃
• mdl: MFCD09754641
• 分子量: 179.175
• InChiKey: JQDUHQARXQIRHF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.111
• 拓扑面积：
  66
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  o-Nitrozimtalkohol 在 氢氧化钾 、 air 、 乙酸酐 、 一水合肼 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 为溶剂， 反应 197.5h， 生成 6,7,12,13-四氢-5H-吲哚并[2,3-a]吡咯并[3,4-c]咔唑-5-酮
  参考文献：
  名称：

  Synthesis of the staurosporine aglycon

  摘要：

  A short synthesis of the staurosporine aglycon (6) is reported, the indolocarbazole skeleton being constructed by an intramolecular Diels-Alder reaction followed by a nitrene-mediated ring closure. The synthesis starts by acylation of ethyl indole-2-acetate with oxalyl chloride. The resulting indole-3-glyoxalyl chloride is quenched with 2-nitrocinnamylamine (29) to give the amide (31). Hydrolysis of the ester group and cyclodehydration then gives the pyranoindolone (35). On heating in bromobenzene, the pyranoindolone 35 undergoes intramolecular Diels-Alder reaction to give, after loss of carbon dioxide and air oxidation, the carbazole 36, which on treatment with triethyl phosphite cyclizes to the staurosporine aglycon. The overall yield from ethyl indole-2-acetate is 22.6%.

  DOI：

  10.1021/jo00033a036
• 作为产物：
  描述：

  (E)-3-(2-硝基苯基)丙-2-烯酸乙酯 在 二异丁基氢化铝 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 以68.6 %的产率得到o-Nitrozimtalkohol
  参考文献：
  名称：

  路易斯碱催化的烯丙醇三氟甲基亚磺酰化：稳定性导向的发散合成

  摘要：

  展示了路易斯碱激活的烯丙醇三氟甲基亚磺酰化的新策略。通过 sigmatropic 重排可控合成结构多样的烯丙基三氟甲砜，并获得了三氟甲亚磺酸酯。这种无金属催化发散转化具有良好的官能团耐受性和生物活性分子的后期修饰。机理研究表明，路易斯碱与N -(三氟甲基亚磺酰基)邻苯二甲酰亚胺相互作用，生成离子对加合物，然后与烯丙醇进行 O-三氟甲基亚磺酰化。

  DOI：

  10.1021/acs.orglett.2c04243

文献信息

• How phenyl makes a difference: mechanistic insights into the ruthenium(<scp>ii</scp>)-catalysed isomerisation of allylic alcohols
  作者：Simone Manzini、Albert Poater、David J. Nelson、Luigi Cavallo、Steven P. Nolan

  DOI：10.1039/c3sc52612g

  日期：——

  [RuCl(η5-3-phenylindenyl)(PPh3)2] (1) has been shown to be a highly active catalyst for the isomerisation of allylic alcohols to the corresponding ketones. A variety of substrates undergo the transformation, typically with 0.25–0.5 mol% of catalyst at room temperature, outperforming commonly-used complexes such as [RuCl(Cp)(PPh3)2] and [RuCl(η5-indenyl)(PPh3)2]. Mechanistic experiments and density functional theory have been employed to investigate the mechanism and understand the effect of catalyst structure on reactivity. These investigations suggest a oxo-π-allyl mechanism is in operation, avoiding intermediate ruthenium hydride complexes and leading to a characteristic 1,3-deuterium shift. Important mechanistic insights from DFT and experiments also allowed for the design of a protocol that expands the scope of the transformation to include primary allylic alcohols.

  [RuCl(η5-3-苯基茚基)(PPh3)2] (1) 已被证明是一种高效的催化剂，用于将烯丙基醇异构化为相应的酮。多种底物在室温下以0.25–0.5 mol%的催化剂量进行转化，其性能优于常用的[RuCl(Cp)(PPh3)2]和[RuCl(η5-茚基)(PPh3)2]等复合物。通过机制实验和密度泛函理论研究，探讨了反应机制并理解了催化剂结构对活性的影响。这些研究提示了一种氧-π-烯丙基机制，避免了中间体钌氢复合物的形成，并导致了特征性的1,3-氘位移。来自DFT和实验的关键机制见解还使得设计了一种协议，将这种转化的应用范围扩展到包括初级烯丙基醇。
• Transfer Hydrogenation of Aldehydes and Ketones with Isopropanol under Neutral Conditions Catalyzed by a Metal–Ligand Bifunctional Catalyst [Cp*Ir(2,2′-bpyO)(H₂O)]
  作者：Rongzhou Wang、Yawen Tang、Meng Xu、Chong Meng、Feng Li

  DOI：10.1021/acs.joc.7b03174

  日期：2018.2.16

  A Cp*Ir complex bearing a functional bipyridonate ligand [Cp*Ir(2,2′-bpyO)(H2O)] was found to be a highly efficient and general catalyst for transfer hydrogenation of aldehydes and chemoselective transfer hydrogenation of unsaturated aldehydes with isopropanol under neutral conditions. It was noteworthy that many readily reducible or labile functional groups such as nitro, cyano, ester, and halide

  发现带有功能联吡啶鎓配体[Cp * Ir（2,2'-bpyO）（H 2 O）]的Cp * Ir配合物是醛转移加氢和不饱和醛化学选择转移加氢的高效通用催化剂在中性条件下用异丙醇。值得注意的是，许多易还原或不稳定的官能团，例如硝基，氰基，酯和卤化物在反应条件下未发生任何变化。此外，该催化体系对于用异丙醇转移酮的氢化显示出高活性。值得注意的是，这项研究展示了金属-配体双功能催化剂在转移加氢方面的新潜力。
• The First Example of Activation of Molecular Oxygen by Nickel in Ni-Al Hydrotalcite: A Novel Protocol for the Selective Oxidation of Alcohols
  作者：B. M. Choudary、M. Lakshmi Kantam、Ateeq Rahman、Ch. Venkat Reddy、K. Koteswara Rao

  DOI：10.1002/1521-3773(20010216)40:4<763::aid-anie7630>3.0.co;2-t

  日期：2001.2.16

  NiO in association with aluminum oxide has been identified by temperature-programmed reduction as the active species in the Ni–Al hydrotalcite catalyst that oxidizes α-ketols as well as benzylic and allylic alcohols to their corresponding carbonyl compounds in oxygen in quantitative yields under mild reaction conditions.

  NiO 与氧化铝结合已通过程序升温还原被确定为 Ni-Al 水滑石催化剂中的活性物质，该催化剂在温和反应下以定量产率将 α-酮醇以及苄醇和烯丙醇氧化成其相应的羰基化合物条件。
• Enantioselective Tandem Oxidation/Michael-Aldol Approaches to Tetrasubstituted Cyclohexanes
  作者：Nirmal K. Rana、Harshit Joshi、Rupesh K. Jha、Vinod K. Singh

  DOI：10.1002/chem.201605999

  日期：2017.2.10

  cyclohexanes in total regio‐, diastereo‐ and enantioselective fashion. The presence of nitro, hydroxy and keto groups in the product provides a wide scope for further structural transformations. Furthermore, the utility of the catalytic process is demonstrated in the context of enantioselective formal synthesis of ABT‐341, a DPP4 inhibitor.

  对映选择性串联迈克尔-羟醛和氧化迈克尔-羟醛方法已经实现了以区​​域，非对映和对映选择性的方式形成各种取代的环己烷。产品中硝基，羟基和酮基的存在为进一步的结构转化提供了广阔的空间。此外，在DPP4抑制剂ABT-341的对映选择性形式合成中证明了催化过程的实用性。
• Hf-MOF catalyzed Meerwein−Ponndorf−Verley (MPV) reduction reaction: Insight into reaction mechanism
  作者：Yamei Lin、Qingxia Bu、Jiaxian Xu、Xiao Liu、Xueping Zhang、Guo-Ping Lu、Baojing Zhou

  DOI：10.1016/j.mcat.2021.111405

  日期：2021.2

  six-membered ring transition state (TS) complex, in which Hf as the center of Lewis stearic acid coordinates with the oxygen of the substrate molecule, thus effectively promoting hydrogen transfer process. Other reactive groups, such as –NO2, C = C, -CN, of inadequate hardness or large steric hindrance are difficult to coordinate with Hf, thus weakening their catalytic effect, which explains the specific selectivity

  Hf-MOF-808通过氢转移策略对羰基化合物的氢化显示出优异的活性和比选择性。其比其他Hf-MOF优异的活性归因于其较差的结晶度，缺陷和较大的比表面积，因此含有更多的路易斯酸碱位点，可促进该反应。进行密度泛函理论（DFT）计算以探索催化机理。结果表明，醇和酮可弥补Hf-MOF的缺陷，形成六元环过渡态（TS）配合物，其中以Hf为路易斯硬脂酸中心的底物与底物分子的氧配位，从而有效促进氢转移过程。其他反应性基团，例如–NO 2硬度不足或位阻大的C = C，-CN很难与Hf配位，因此减弱了它们的催化作用，这解释了Hf-MOF-808还原羰基的选择性。