2-cyclohexyl-1-(naphthalen-1-yl)ethan-1-one

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-cyclohexyl-1-(naphthalen-1-yl)ethan-1-one
• 英文别名: 2-Cyclohexyl-1-naphthalen-1-ylethanone
• 化学式: C₁₈H₂₀O
• mdl: MFCD19144817
• 分子量: 252.356
• InChiKey: YAXPZJFKFWBXRP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.388
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  1-(cyclohexylethynyl)naphthalene 在 水 、 silver trifluoromethanesulfonate 作用下， 以 氯苯 为溶剂， 以71 %的产率得到2-cyclohexyl-1-(naphthalen-1-yl)ethan-1-one
  参考文献：
  名称：

  10.1002/cctc.202400735

  摘要：

  In the absence of directing auxiliaries, catalytic addition of nucleophiles to unactivated alkynes with accurate control of regioselectivity remains an ongoing challenge in organic chemistry. Herein, we realized a Ag‐catalysed regiospecific hydration process of unactivated alkynes. Computational investigations offered insights into the origin of the regiochemical outcome. The practicability and efficacy of the protocol was exemplified by its simple reaction conditions without incorporation of acidic additives, as well as the toler‐ance of a wide range of alkynes equipped with various functional groups, leading to the ketone products in up to 98% yield. Direct modification of bioactive organic molecules and gram‐scale experiments further showcased the application potential of the strategy. The catalyst control principles are expected to advance efforts towards the development of general site‐selective addition of nucleophile to unsaturated substrates, removing the requirement for neighboring activating groups.

  DOI：

  10.1002/cctc.202400735

文献信息

• Ruthenium-Catalyzed Direct Cross-Coupling of Secondary Alcohols to β-Disubstituted Ketones
  作者：Subramanian Thiyagarajan、Chidambaram Gunanathan

  DOI：10.1055/s-0037-1611912

  日期：2019.11

  prevalent in biologically active compounds and in pharmaceuticals. A ruthenium-catalyzed direct synthesis of β-disubstituted ketones by cross-coupling of two different secondary alcohols is reported. This new protocol was applied to the synthesis of variety of β-disubstituted ketones from various cyclic, acyclic, symmetrical, and unsymmetrical secondary alcohols. An amine–amide metal–ligand cooperation

  β-二取代的酮官能团在生物活性化合物和药物中很普遍。报道了通过两种不同仲醇的交叉偶联在钌催化下直接合成 β-二取代酮。这一新协议被应用于从各种环状、无环、对称和不对称仲醇合成各种 β-二取代酮。Ru催化剂中的胺-酰胺金属-配体合作促进了选择性序列中共价键的活化和形成以提供产物。动力学和氘标记实验表明脂肪醇比苄基仲醇氧化得更快。在机械和动力学研究的基础上提出了一种合理的机制。水和 H2 是这种仲醇选择性交叉偶联的唯一副产物。1 引言 2 醇的催化自偶联或交叉偶联和选择性挑战 3 β-二取代酮合成的最新进展 4 钌催化仲醇交叉偶联的范围 5 机理研究和建议的机理 6 结论
• Catalytic Cross-Coupling of Secondary Alcohols
  作者：Subramanian Thiyagarajan、Chidambaram Gunanathan

  DOI：10.1021/jacs.9b00025

  日期：2019.3.6

  assimilating to provide the cross-coupled products. Reactions are sensitive to steric hindrance. This new C-C bond forming methodology requires low catalyst load and catalytic amount of base. Notably, the reaction produces H2 and H2O as the only byproducts making the protocol greener, atom economical and environmentally benign.

  在此，报道了一种前所未有的钌（II）催化的两种不同仲醇与 β-二取代酮的直接交叉偶联。环状、酰基、对称和不对称仲醇与芳香族苄基仲醇选择性偶联以提供酮产品。单一催化剂氧化两种仲醇以提供选择性 β-二取代酮，以扩大该催化协议的范围。通过在 Ru-MACHO 催化剂中起作用的胺-酰胺金属-配体合作，键活化和键形成反应的数量以选择性顺序发生。还观察到产物诱导的非对映选择性。动力学和氘标记实验表明，脂肪族仲醇比苄类仲醇进行氧化反应更快，选择性同化以提供交叉耦合产品。反应对位阻敏感。这种新的 CC 键形成方法需要低催化剂负载和催化量的碱。值得注意的是，该反应产生 H2 和 H2O 作为唯一的副产品，使该协议更加绿色、原子经济和环境友好。
• Divergent Synthesis of Alcohols and Ketones via Cross‐Coupling of Secondary Alcohols under Manganese Catalysis
  作者：Feixiang Sun、Jiamin Huang、Zhihong Wei、Conghui Tang、Weiping Liu

  DOI：10.1002/anie.202303433

  日期：2023.6.26

  A manganese-catalyzed cross-coupling of two secondary alcohols in a divergent synthesis of either γ-disubstituted alcohols or β-disubstituted ketones is herein reported. A wide range of different alcohols could undergo the cross-coupling process smoothly and furnish the corresponding products by using the same catalyst, with overall moderate to good yields.

  本文报道了在 γ-二取代醇或 β-二取代酮的不同合成中锰催化的两种仲醇的交叉偶联。多种不同的醇可以顺利地进行交叉偶联过程，并通过使用相同的催化剂提供相应的产品，总体收率中等至良好。
• Selective control of secondary alcohols upgrading using Ir-catalyzed cross-coupling strategy
  作者：Siqi Yang、Zeye Lu、Jiale Ji、Qingshu Zheng、Tao Tu

  DOI：10.1007/s11426-023-1843-8

  日期：2024.3

  The selective coupling of alcohols is a fascinating yet challenging approach for upgrading alcohols. Herein, we accomplished the controlled production of β-disubstituted ketones or upgraded secondary alcohols via the Ir-catalyzed cross-coupling of secondary alcohols in excellent yields with broad substrate scopes. This selective control was achieved by using an in-situ generated mono-NHC-Ir or a tris-NHC-Ir

  醇的选择性偶联是一种令人着迷但具有挑战性的醇升级方法。在此，我们通过Ir 催化的仲醇交叉偶联，实现了β-二取代酮或升级仲醇的受控生产，具有优异的产率和广泛的底物范围。这种选择性控制是通过分别使用原位生成的单-NHC-Ir或三-NHC-Ir络合物作为催化剂来实现的。机理研究表明，这些双功能催化剂的脱氢和加氢能力之间的微妙平衡对于实现不同的选择性至关重要。三-NHC-Ir络合物有效地促进了醇的脱氢和中间体的氢化，从而产生了所需的升级仲醇。相反，单-NHC-Ir络合物的高脱氢能力促进了形成的仲醇转化回酮。
• Cu(II) Promoted C(sp³)−H Activation in Unactivated Cycloalkanes: Oxo‐Alkylation of Styrenes to Synthesize <i>β‐</i>Disubstituted Ketones
  作者：Krishna Mohan Das、Adwitiya Pal、Lakshmi Surya T、Lisa Roy、Arunabha Thakur

  DOI：10.1002/chem.202303776

  日期：2024.2.7

  We report the Cu(II) catalyzed synthesis of β‐disubstituted ketones from styrene via oxo‐alkylation with unactivated cycloalkanes as the alkylating agent in presence of tert‐butylhydroperoxide (TBHP) and 1‐methylimidazole as oxidant and base respectively. β‐disubstituted ketones are known to be synthesized by using either expensive Ru/Ir complexes, or low‐cost metal complexes (e. g., Fe, Mn) with activated species like aldehyde, acid, alcohol, or phthalimide derivatives as the alkylating agent, however, use of unactivated cycloalkanes directly as the alkylating agent remains challenging. A wide range of aliphatic C−H substrates as well as various olefinic arenes and heteroarene (35 substrates including 14 new substrates) are well‐tolerated in this method. Hammett analysis shed more light on the substitution effect in the olefinic part on the overall mechanism. Furthermore, the controlled experiments, kinetic isotope effect study, and theoretical calculations (DFT) enable us to gain deeper insight of mechanistic intricacies of this new simple and atom‐economic methodology.

  摘要 我们报告了在叔丁基过氧化氢（TBHP）和 1-甲基咪唑分别作为氧化剂和碱的存在下，以未活化的环烷烃为烷基化剂，通过氧化-烷基化反应催化苯乙烯合成 β-二取代酮的情况。众所周知，使用昂贵的 Ru/Ir 复合物或低成本的金属复合物（如铁、锰）与醛、酸、醇或邻苯二甲酰亚胺衍生物等活化物作为烷化剂，可以合成 β-二取代酮，但是直接使用未活化的环烷烃作为烷化剂仍然具有挑战性。在这种方法中，广泛的脂肪族 C-H 底物以及各种烯烃炔和杂芳烃（35 种底物，包括 14 种新底物）都能很好地耐受。Hammett 分析进一步揭示了烯烃部分的取代效应对整个机理的影响。此外，对照实验、动力学同位素效应研究和理论计算（DFT）使我们能够更深入地了解这种简单而原子经济的新方法的复杂机理。