2-Adamantyl phenyl ketone | 68157-27-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-Adamantyl phenyl ketone
• 英文别名: 2-Adamantyl(phenyl)methanone
• CAS: 68157-27-7
• 化学式: C₁₇H₂₀O
• 分子量: 240.345
• InChiKey: NELUDAFMEHSVMO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.588
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-Adamantyl phenyl ketone 在 lithium diisopropyl amide 作用下， 以 乙醚 为溶剂， 反应 0.75h， 以10%的产率得到2-adamantyl(phenyl)methanol
  参考文献：
  名称：

  Face Selection in the Capture of Anionic Carbon

  摘要：

  Several reactions of 2-(5-phenyladamantyl) derivatives have been examined with the objective of determining the stereochemistry of addition of electrophiles to a trigonal center Ct carrying a full or partial negative charge. These reactions included the carbonation and bromination of the 2-lithioadamantane(s) attack at the zu face was found to be predominant. Methylation of 5-phenyl-2-adamantanone with either methyllithium or lithium dimethylcuprate gave mixtures of the methyl alcohols in which the E-isomer is the main product. Attempts to study the reactions of the enolate anion derived from the (E)- and (Z)-phenyl 2-(5-phenyladamantyl) ketones 7-Ph were not successful: bromination could not be forced at all, and methylation and protonation occur at oxygen. The enol ether and enol were studied also; brominations of these neutral species occur at the zu face. It is concluded that even the imposition of negative charge upon the trigonal center does not engender the type of hyperconjugation envisioned by Anh in the capture of electrophiles. Protonation of the enol ether led to an equilibrium mixture of ketones 7-Ph; protonation of the enol itself gave an excess of the E-isomer. Possible reasons for this unexpected outcome are discussed.

  DOI：

  10.1021/jo00091a009
• 作为产物：
  描述：

  Benzyloxy (phenyl)methylidene adamantane 在 tris(p-bromophenylammoniumyl) hexachloroantimonate 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 2-Adamantyl phenyl ketone
  参考文献：
  名称：

  Electron-transfer induced conversion of enol-ethers into ketones

  摘要：

  DOI：

  10.1016/s0040-4039(00)95236-5

文献信息

• Synergistic Activation of Amides and Hydrocarbons for Direct C(sp ³ )–H Acylation Enabled by Metallaphotoredox Catalysis
  作者：Geun Seok Lee、Joonghee Won、Seulhui Choi、Mu‐Hyun Baik、Soon Hyeok Hong

  DOI：10.1002/anie.202004441

  日期：2020.9.21

  amides as stable and readily accessible acyl surrogates. N‐acylsuccinimides served as efficient acyl reagents for the streamlined synthesis of synthetically useful ketones from simple C(sp3)−H substrates. Detailed mechanistic investigations using both computational and experimental mechanistic studies were performed to construct a detailed and complete catalytic cycle. The origin of the superior reactivity

  在催化中，无所不在的热力学稳定的酰胺和脂族C（sp 3）-H键的各种功能化利用一直是挑战。特别地，尚未实现两个官能团之间的直接偶联。在这里，我们报告了两个具有挑战性的键，酰胺C-N和未活化的脂肪族C（sp 3）-H，通过金属光催化还原催化直接酰化脂肪族的CH-H键，利用酰胺作为稳定且易于接近的酰基替代物的协同活化。N-酰基琥珀酰亚胺可作为有效的酰基试剂，用于从简单C（sp 3）简化合成有用的酮的合成）-H基板。使用计算和实验机理研究进行了详细的机理研究，以构建详细而完整的催化循环。发现N-酰基琥珀酰亚胺比其他更具反应性的酰基源（如酰氯）具有更高反应活性的起源是一种罕见的反应途径，其始于在氧化添加酰基底物之前的CH活化。
• McMurry intermolecular cross-coupling between an ester and a ketone: scope and limitations
  作者：Stéphane Sabelle、Jérôme Hydrio、Eric Leclerc、Charles Mioskowski、Pierre-Yves Renard

  DOI：10.1016/s0040-4039(02)00617-2

  日期：2002.5

  were faced with the synthesis of sterically hindered benzylic enol ethers. This issue was solved via the use of an intermolecular McMurry cross-coupling between an ester and a ketone. In this article, together with the synthesis of the chemiluminescent probe, the scope and limitations of this low valent titanium based carboncarbon double bond formation are discussed.

  在关于合成用于检测硫醇的带有二氧杂环丁烷的化学发光探针的研究过程中，我们面临着位阻苄基烯醇醚的合成。通过使用酯和酮之间的分子间McMurry交叉偶联解决了这个问题。在本文中，连同化学发光探针的合成，讨论了这种低价钛基碳碳双键形成的范围和局限性。
• An Investigation of the Yang Photocyclization Reaction in the Solid State:  Asymmetric Induction Studies and Crystal Structure−Reactivity Relationships
  作者：Mordechai Leibovitch、Gunnar Olovsson、John R. Scheffer、James Trotter

  DOI：10.1021/ja9823013

  日期：1998.12.1

  investigated in the solid state and solution. In both media, ketones bearing methyl substituents α to the benzoyl group undergo stereoselective Yang photocyclization to afford endo-arylcyclobutanols. Quantum yield and quenching studies in solution show that the reactions are efficient triplet-mediated processes. Asymmetric induction studies were carried out by providing the reactants with carboxylic acid

  已在固态和溶液中研究了具有基本顺-4-叔丁基-1-苯甲酰基环己烷或 2-苯甲酰基金刚烷结构的 16 种酮的 Norrish/Yang II 型光化学。在这两种介质中，带有甲基取代基α到苯甲酰基的酮经历立体选择性阳光环化以提供内芳基环丁醇。溶液中的量子产率和猝灭研究表明，这些反应是有效的三重态介导过程。不对称诱导研究是通过为反应物提供羧酸取代基来进行的，“离子手性助剂”通过与旋光胺形成盐而连接到这些羧酸取代基上。溶液中的盐（总共 17 种）的辐照得到外消旋环丁醇，但在结晶状态下，获得了中等至接近定量的对映体过量。对 10 种中性酮和四种盐成功进行了单晶 X 射线衍射研究。这允许识别反应性γ-氢原子并...
• Organocatalytic C−H Functionalization of Simple Alkanes
  作者：Fen Su、Fengfei Lu、Kun Tang、Xiaokang Lv、Zhongfu Luo、Fengrui Che、Hongyan Long、Xingxing Wu、Yonggui Robin Chi

  DOI：10.1002/anie.202310072

  日期：2023.11.6

  functionalization/acylation of strong aliphatic C(sp3)-H bonds is disclosed via an N-heterocyclic carbene (NHC)-catalyzed dehydrogenative coupling of aldehydes with simple alkanes. The inert aliphatic C−H bonds are efficiently cleaved through intermolecular hydrogen atom transfer, providing an alternative organocatalytic approach for alkane C−H functionalization under transition metal- and light free

  公开了通过醛与简单烷烃的N-杂环卡宾(NHC)催化的脱氢偶联强脂肪族C(sp 3 )-H键的有机催化直接官能化/酰化。惰性脂肪族CH键通过分子间氢原子转移有效裂解，为在过渡金属和无光条件下烷烃CH官能化提供了另一种有机催化方法。
• Ultrafast Photoelimination of Nitrogen from Upper Excited States of Diazoalkanes and the Fate of Carbenes Formed in the Reaction
  作者：Vedran Brusar、Mateo Forjan、Ivan Ljubić、Marija Alešković、Kristin Becker、Silvije Vdović

  DOI：10.1021/acs.joc.2c02875

  日期：——

  delivers the triplet carbene by intersystem crossing (ISC). Singlet car-2 does not undergo ISC but reacts in the intermolecular insertion reactions into C–H bonds. Car-3 has an α-C–H bond next to the carbene center and reacts rapidly in the intramolecular C–H insertion reaction to deliver alkene, precluding its detection by fs-TA. However, the isolation of ketone photoproducts from 3 is highly indicative of

  通过瞬态吸收光谱 (TA) 分别研究了二苯基重氮甲烷1和苯基 1- 和 2-金刚烷基重氮甲烷2和3的光化学反应性。在 anti-Kasha 超快光化学反应中，UV 激发后N 2发生光消除，从上层激发单线态产生单线态卡宾，在1和2的情况下，fs-TA 检测到了这些卡宾。卡宾的反应性与卡宾中心的取代基有关。非极性溶剂中的单线态car-1通过系统间交叉 (ISC) 传递三线态卡宾。单线车-2不经历 ISC，但在 C-H 键的分子间插入反应中发生反应。Car-3在卡宾中心旁边有一个 α-C-H 键，并在分子内 C-H 插入反应中快速反应以传递烯烃，从而阻止其被 fs-TA 检测。然而，从3中分离出酮光产物高度表明了三重态car-3的中间体形成。1-3的S 1​​ –S 3态的 TA 光谱使用时间相关的密度泛函理论计算，而二阶多构型微扰理论用于相应的单线态和三线态卡宾的吸收光谱。建模和测量的光谱非常