Methyl 6-((diethylcarbamoyl)oxy)-2-naphthoate | 1201593-94-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: Methyl 6-((diethylcarbamoyl)oxy)-2-naphthoate
• 英文别名: methyl 6-(diethylcarbamoyloxy)naphthalene-2-carboxylate
• CAS: 1201593-94-3
• 化学式: C₁₇H₁₉NO₄
• 分子量: 301.342
• InChiKey: FCNZYBUASPDYGD-UHFFFAOYSA-N

物化性质

• 沸点：
  433.8±27.0 °C(Predicted)
• 密度：
  1.177±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.47
• 重原子数：
  22.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  55.84
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  Methyl 6-((diethylcarbamoyl)oxy)-2-naphthoate 在 二氯化双(三环己基膦)镍(II) 、 1,1,3,3-四甲基二硅氧烷 、 K₃PO₄ 作用下， 以 甲苯 为溶剂， 反应 15.0h， 以91%的产率得到2-萘甲酸甲酯
  参考文献：
  名称：

  Cine Substitution of Arenes Using the Aryl Carbamate as a Removable Directing Group

  摘要：

  An efficient and controlled means to achieve a rare cine substitution of arenes is reported. The methodology relies on the strategic use of aryl O-carbamates as readily removable directing groups for arene functionallzation. The removal of aryl carbamates is achieved by employing an airstable Ni(II) precatalyst, along with an inexpensive reducing agent, to give synthetically useful yields across a range of substrates. The net cine substitution process offers a new strategy for analogue synthesis, which complements the well-established logic for achieving arene functionalization by ipso substitution.

  DOI：

  10.1021/ol301275u
• 作为产物：
  描述：

  6-羟基-2-萘甲酯 、 N,N-二乙基氯甲酰胺 在 sodium hydride 作用下， 以 乙二醇二甲醚 、 mineral oil 为溶剂， 反应 11.17h， 以87%的产率得到Methyl 6-((diethylcarbamoyl)oxy)-2-naphthoate
  参考文献：
  名称：

  Suzuki−Miyaura Coupling of Aryl Carbamates, Carbonates, and Sulfamates

  摘要：

  The first Suzuki-Miyaura cross-couplings of carbamates, carbonates, and sulfamates is described. The method provides a powerful means of using simple derivatives of phenol as precursors to polysubstituted aromatic compounds, as exemplified by a concise synthesis of the anti-inflammatory drug flurbiprofen.

  DOI：

  10.1021/ja906477r

文献信息

• Suzuki−Miyaura Cross-Coupling of Aryl Carbamates and Sulfamates: Experimental and Computational Studies
  作者：Kyle W. Quasdorf、Aurora Antoft-Finch、Peng Liu、Amanda L. Silberstein、Anna Komaromi、Tom Blackburn、Stephen D. Ramgren、K. N. Houk、Victor Snieckus、Neil K. Garg

  DOI：10.1021/ja200398c

  日期：2011.4.27

  The first Suzuki-Miyaura cross-coupling reactions of the synthetically versatile aryl O-carbamate and O-sulfamate groups are described. The transformations utilize the inexpensive, bench-stable catalyst NiCl2(PCy3)(2) to furnish biaryls in good to excellent yields. A broad scope for this methodology has been demonstrated. Substrates with electron-donating and electron-withdrawing groups are tolerated, in addition to those that possess ortho substituents. Furthermore, heteroaryl substrates may be employed as coupling partners. A computational study providing the full catalytic cycles for these cross-coupling reactions is described. The oxidative addition with carbamates or sulfamates occurs via a five-centered transition state, resulting in the exclusive cleavage of the aryl C-O bond. Water is found to stabilize the Ni-carbamate catalyst resting state, which thus provides rationalization of the relative decreased rate of coupling of carbamates. Several synthetic applications are presented to showcase the utility of the methodology in the synthesis of polysubstituted aromatic compounds of natural product and bioactive molecule interest.