γ-(trimethylsilyl)butyro-2-naphthone | 153489-20-4

• 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: γ-(trimethylsilyl)butyro-2-naphthone
• 英文别名: 1-Naphthalen-2-yl-4-trimethylsilylbutan-1-one
• CAS: 153489-20-4
• 化学式: C₁₇H₂₂OSi
• 分子量: 270.447
• InChiKey: IGSOMROQGQPJFW-UHFFFAOYSA-N

物化性质

• 沸点：
  380.4±25.0 °C(Predicted)
• 密度：
  0.989±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.14
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 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：

  γ-(trimethylsilyl)butyro-2-naphthone 以 氘代乙腈 为溶剂， 反应 100.0h， 以19%的产率得到1,4-双(2-萘基)-1,4-丁二酮
  参考文献：
  名称：

  Exploratory Studies of H-Atom Abstraction and Silyl-Transfer Photoreactions of Silylalkyl Ketones and (Silylalkyl)phthalimides

  摘要：

  Exploratory studies have been conducted to probe competitive H-atom abstraction and SET-promoted, silyl-transfer reactions of excited states of silylalkyl ketones and (silylalkyl)phthalimides. Photochemical investigations with the (silylalkyl)phthalimides have demonstrated that typical gamma-H atom abstraction reactions occur upon irradiation in less polar and less silophilic solvents. In contrast, irradiation of these substances in polar-protic-silophilic solvents results in product formation via pathways involving SET-induced desilylation. Photoreactions of silylamido-aryl ketones in either nonsilophilic or silophilic solvents take place almost exclusively by sequential SET silyl-transfer routes to produce azetidine products. Finally, the chemical selectivities of photochemical reactions of silylpropyl-aryl ketones appear to depend on medium polarity and silophilicity. Irradiation of these substrates in less polar-nonsilophilic solvents leads to almost exclusive formation of acetophenone and vinyltrimethylsilane in essentially equal yields by a reaction pathway initiated by gamma-H atom abstraction and 1,4-biradical fragmentation. However, irradiation of these substances in polar-silophilic solvents produces acetophenone and vinyltrimethylsilane in an ca. 1.7:1 ratio reflecting the fact that a silyl-transfer pathway competes with H-atom abstraction under these conditions.

  DOI：

  10.1021/jo9522623
• 作为产物：
  描述：

  2-萘甲酰氯 在 4-二甲氨基吡啶 、 [Pd(IPr)(cin)Cl] 、 caesium carbonate 、 三乙胺 作用下， 以 水 、 甲苯 为溶剂， 反应 16.0h， 生成 γ-(trimethylsilyl)butyro-2-naphthone
  参考文献：
  名称：

  钯催化的酯基烷基交叉偶联中的可切换选择性

  摘要：

  公开了Pd催化的苯基酯和烷基硼烷的交叉偶联。通过交换催化剂，可以选择性地接近两种反应模式。使用Pd-NHC系统，可以通过激活C（酰基）-O键进行的Suzuki-Miyaura反应，以高收率制备烷基酮。使用Pd-二氯乙烯催化剂可使烷基化的芳烃通过CO挤出的修饰途径合成。讨论了这种分歧偶联策略的应用以及可切换选择性的起源。

  DOI：

  10.1021/acs.orglett.8b01646

文献信息

• The operation of H-atom and TMS-group transfer processes in the photochemistry of silylamidoalkyl- and silylalkyl-ketones and -phthalimides
  作者：Yean Jang Lee、Chao Pin Lee、Yoon Tag Jeon、Patrick S. Mariano、Ung Chan Yoon、Dong Uk Kim、Jack C. Kim、Jong Gun Lee

  DOI：10.1016/s0040-4039(00)73797-x

  日期：1993.9
• Exploratory Studies of H-Atom Abstraction and Silyl-Transfer Photoreactions of Silylalkyl Ketones and (Silylalkyl)phthalimides
  作者：Yean Jang Lee、Rong Ling、Patrick S. Mariano、Ung Chan Yoon、Dong Uk Kim、Sun Wha Oh

  DOI：10.1021/jo9522623

  日期：1996.1.1

  Exploratory studies have been conducted to probe competitive H-atom abstraction and SET-promoted, silyl-transfer reactions of excited states of silylalkyl ketones and (silylalkyl)phthalimides. Photochemical investigations with the (silylalkyl)phthalimides have demonstrated that typical gamma-H atom abstraction reactions occur upon irradiation in less polar and less silophilic solvents. In contrast, irradiation of these substances in polar-protic-silophilic solvents results in product formation via pathways involving SET-induced desilylation. Photoreactions of silylamido-aryl ketones in either nonsilophilic or silophilic solvents take place almost exclusively by sequential SET silyl-transfer routes to produce azetidine products. Finally, the chemical selectivities of photochemical reactions of silylpropyl-aryl ketones appear to depend on medium polarity and silophilicity. Irradiation of these substrates in less polar-nonsilophilic solvents leads to almost exclusive formation of acetophenone and vinyltrimethylsilane in essentially equal yields by a reaction pathway initiated by gamma-H atom abstraction and 1,4-biradical fragmentation. However, irradiation of these substances in polar-silophilic solvents produces acetophenone and vinyltrimethylsilane in an ca. 1.7:1 ratio reflecting the fact that a silyl-transfer pathway competes with H-atom abstraction under these conditions.
• Switchable Selectivity in the Pd-Catalyzed Alkylative Cross-Coupling of Esters
  作者：Jeanne Masson-Makdissi、Jaya Kishore Vandavasi、Stephen G. Newman

  DOI：10.1021/acs.orglett.8b01646

  日期：2018.7.6

  The Pd-catalyzed cross-coupling of phenyl esters and alkyl boranes is disclosed. Two reaction modes are rendered accessible in a selective fashion by interchange of the catalyst. With a Pd–NHC system, alkyl ketones can be prepared in good yields via a Suzuki–Miyaura reaction proceeding by activation of the C(acyl)–O bond. Use of a Pd–dcype catalyst enables alkylated arenes to be synthesized by a modified

  公开了Pd催化的苯基酯和烷基硼烷的交叉偶联。通过交换催化剂，可以选择性地接近两种反应模式。使用Pd-NHC系统，可以通过激活C（酰基）-O键进行的Suzuki-Miyaura反应，以高收率制备烷基酮。使用Pd-二氯乙烯催化剂可使烷基化的芳烃通过CO挤出的修饰途径合成。讨论了这种分歧偶联策略的应用以及可切换选择性的起源。