2-(adamantan-2-yl)-1-phenylethan-1-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(adamantan-2-yl)-1-phenylethan-1-one
• 英文别名: 4-Adamantylacetophenone；2-(2-adamantyl)-1-phenylethanone
• 化学式: C₁₈H₂₂O
• 分子量: 254.372
• InChiKey: HOSRODGIJVMHEP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.61
• 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-(adamantan-2-yl)-1-phenylethan-1-one 、 2-苯基丙烯酸乙酯 在 [Ir(dF(CF₃)ppy)₂(dtbbpy)](PF₆) 、 三(五氟苯基)硼烷 、 2,6-二甲基-4-苯基-1,4-二氢吡啶-3,5-二羧酸二乙酯 、 对甲苯磺酸 作用下， 以 二甲基亚砜 为溶剂， 反应 60.0h， 生成 5-(((1r,3r,5r,7r)-adamantan-2-yl)methyl)-3,5-diphenyldihydrofuran-2(3H)-one 、 5-(((1r,3r,5r,7r)-adamantan-2-yl)methyl)-3,5-diphenyldihydrofuran-2(3H)-one
  参考文献：
  名称：

  用α，β-不饱和酯对羰基化合物进行光诱导的乌磺隆加成，可形成多取代的γ-内酯

  摘要：

  本文我们报告的光诱导分子间极性转换添加具有α，β不饱和酯的芳族酮/醛的通过羰自由基中间体。分子内酯交换后，很容易获得各种γ-内酯衍生物。机理研究表明，汉茨酯具有重要的作用，它既可以作为电子也可以作为质子供体。

  DOI：

  10.1039/d0cc05306f
• 作为产物：
  描述：

  2-金刚烷醇 在 potassium tert-butylate 、 氢碘酸 、 sodium iodide 、 iron(II) bromide 作用下， 以 二甲基亚砜 为溶剂， 反应 49.0h， 生成 2-(adamantan-2-yl)-1-phenylethan-1-one
  参考文献：
  名称：

  Reactions of 2-Iodo- and 1,2-Dihaloadamantanes with Carbanions in DMSO by the S_RN1 Mechanism

  摘要：

  The reaction of 2-iodoadamantane (1) with the potassium enolate of acetophenone (2) did not occur in the dark but succeeded under irradiation or in the presence of FeBr2 to give the substitution product 3 in 62% and 88% yields, respectively. The photostimulated reaction was inhibited by p-dinitrobenzene (p-DNB). There was no reaction of 1 with the anion of nitromethane (4) in the dark or under irradiation. However, 4 reacted with 1 in the presence of acetone enolate ion (entrainment reaction) to yield 88% of the substitution product 2-adamantylnitromethane (5). The photostimulated reaction of 1 with anthrone (6), 2-naphthyl methyl ketone (9), and N-acetylthiomorpholine (11) anions afforded the substitution compounds 7 (37%), 10 (32%), and 12 (20%), respectively. There was no reaction of 1-chloro-2-iodoadamantane (13) with 2 in the dark (2 h), but under irradiation (5 min) it yielded 52% of the monosubstitution product alpha-(1-chloro-2-adamantyl)acetophenone (14). Under longer irradiation time (3 h), the same yield of 14 (52%) was obtained but the disubstitution product 15 was formed in 45% yield. Product 15 was also formed in the photostimulated reaction of 14 with 2. 2-Chloro-1-iodoadamantane (18) did not read with 2 in the dark (2 h), but the photostimulated reaction yielded the monosubstitution product alpha-(2-chloro-1-ladamantyl)acetophenone (19) in 53% and 15 in 4% yield. Products 14 and 19 are intermediates in the formation of 15 in these reactions. There was a slow dark reaction of 1,2-diiodoadamantane (20) with 4 in the presence of acetone enolate ion to afford the iodomonosubstitution compound 21 (40%) and the disubstitution product 22 (13%). The photostimulated reaction (25 min) gave 21 (48%) and 22 (41%). On the other hand, after 3 h of irradiation, only traces of 21 could be detected (<5%) and the product distribution consisted mainly of 22. The iodomonosubstitution product 21 is an intermediate in these reactions.

  DOI：

  10.1021/jo990156l

文献信息

• Aldehydes as Alkylating Agents for Ketones
  作者：Sofiya A. Runikhina、Oleg I. Afanasyev、Klim Biriukov、Dmitry S. Perekalin、Martin Klussmann、Denis Chusov

  DOI：10.1002/chem.201904605

  日期：2019.12.18

  halides. The developed reductive alkylation reaction proceeds in the presence of the commercially available ruthenium catalyst [(cymene)RuCl2 ]2 (as low as 250 ppm) and carbon monoxide as the reducing agent. The reaction works well for a broad substrate scope, including aromatic and aliphatic aldehydes and ketones. It can be carried out without a solvent and often gives nearly quantitative yields of the

  提出了普通和无毒的醛作为酮烷基化的试剂，而不是致癌的烷基卤化物。所开发的还原烷基化反应在市售钌催化剂[（cymene）RuCl 2] 2（低至250ppm）和一氧化碳作为还原剂的存在下进行。该反应适用于广泛的底物范围，包括芳族和脂族醛和酮。它可以在没有溶剂的情况下进行，通常可以得到几乎定量的产物收率。这种简单，经济高效的方法不仅在实验室应用中而且对于工业界都很有希望，因为工业界将一氧化碳作为大规模的废品生产。
• Ruthenium-Catalyzed α-Alkylation of Ketones Using Secondary Alcohols to β-Disubstituted Ketones
  作者：Subramanian Thiyagarajan、Raman Vijaya Sankar、Chidambaram Gunanathan

  DOI：10.1021/acs.orglett.0c02787

  日期：2020.10.16

  An assortment of aromatic ketones was successfully functionalized with a variety of unactivated secondary alcohols that serve as alkylating agents, providing β-disubstituted ketone products in good to excellent yields. Remarkably, challenging substrates such as simple acetophenone derivatives are effectively alkylated under this ruthenium catalysis. The substituted cyclohexanol compounds displayed

  各种各样的芳香族酮已成功地用各种未活化的仲醇作为烷基化剂进行了功能化，从而以良好的产率提供了β-二取代的酮类产品。值得注意的是，在这种钌催化下，具有挑战性的底物（例如简单的苯乙酮衍生物）可以有效地烷基化。取代的环己醇化合物显示出产物诱导的非对映选择性。机理研究表明，氢借入途径参与了这些烷基化反应。值得注意的是，这种选择性的催化C–C键形成反应仅需极少量的催化剂和碱，即可产生H 2 O作为唯一的副产物，因此该方案具有吸引力且对环境无害。
• Heterogeneously catalyzed direct cross-coupling of secondary alcohols to β-disubstituted ketones by Cu/γ-Al2O3
  作者：Jie Jiang、Yuqiang Ding

  DOI：10.1016/j.ica.2022.120830

  日期：2022.5
• Photoinduced umpolung addition of carbonyl compounds with α,β-unsaturated esters enables the polysubstituted γ-lactone formation
  作者：Jia-Yi Gu、Wei Zhang、Seth R. Jackson、Yan-Hong He、Zhi Guan

  DOI：10.1039/d0cc05306f

  日期：——

  herein report the photoinduced intermolecular umpolung addition of aromatic ketones/aldehydes with α,β-unsaturated esters via ketyl radical intermediates. Following an intramolecular transesterification, a variety of γ-lactone derivatives are readily accessed. Mechanistic investigations demonstrate the significant role of Hantzsch ester, which serves both as the electron and proton donor.

  本文我们报告的光诱导分子间极性转换添加具有α，β不饱和酯的芳族酮/醛的通过羰自由基中间体。分子内酯交换后，很容易获得各种γ-内酯衍生物。机理研究表明，汉茨酯具有重要的作用，它既可以作为电子也可以作为质子供体。
• Reactions of 2-Iodo- and 1,2-Dihaloadamantanes with Carbanions in DMSO by the S_RN1 Mechanism
  作者：Andrés E. Lukach、Roberto A. Rossi

  DOI：10.1021/jo990156l

  日期：1999.8.1

  The reaction of 2-iodoadamantane (1) with the potassium enolate of acetophenone (2) did not occur in the dark but succeeded under irradiation or in the presence of FeBr2 to give the substitution product 3 in 62% and 88% yields, respectively. The photostimulated reaction was inhibited by p-dinitrobenzene (p-DNB). There was no reaction of 1 with the anion of nitromethane (4) in the dark or under irradiation. However, 4 reacted with 1 in the presence of acetone enolate ion (entrainment reaction) to yield 88% of the substitution product 2-adamantylnitromethane (5). The photostimulated reaction of 1 with anthrone (6), 2-naphthyl methyl ketone (9), and N-acetylthiomorpholine (11) anions afforded the substitution compounds 7 (37%), 10 (32%), and 12 (20%), respectively. There was no reaction of 1-chloro-2-iodoadamantane (13) with 2 in the dark (2 h), but under irradiation (5 min) it yielded 52% of the monosubstitution product alpha-(1-chloro-2-adamantyl)acetophenone (14). Under longer irradiation time (3 h), the same yield of 14 (52%) was obtained but the disubstitution product 15 was formed in 45% yield. Product 15 was also formed in the photostimulated reaction of 14 with 2. 2-Chloro-1-iodoadamantane (18) did not read with 2 in the dark (2 h), but the photostimulated reaction yielded the monosubstitution product alpha-(2-chloro-1-ladamantyl)acetophenone (19) in 53% and 15 in 4% yield. Products 14 and 19 are intermediates in the formation of 15 in these reactions. There was a slow dark reaction of 1,2-diiodoadamantane (20) with 4 in the presence of acetone enolate ion to afford the iodomonosubstitution compound 21 (40%) and the disubstitution product 22 (13%). The photostimulated reaction (25 min) gave 21 (48%) and 22 (41%). On the other hand, after 3 h of irradiation, only traces of 21 could be detected (<5%) and the product distribution consisted mainly of 22. The iodomonosubstitution product 21 is an intermediate in these reactions.