喹啉-6-基二甲基氨基磺酸酯 | 1286763-01-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 中文名称: 喹啉-6-基二甲基氨基磺酸酯
• 英文名称: quinolin-6-yl dimethylsulfamate
• 英文别名: quinolin-6-yl N,N-dimethylsulfamate
• CAS: 1286763-01-6
• 化学式: C₁₁H₁₂N₂O₃S
• 分子量: 252.294
• InChiKey: XBTRYUDNJISFHU-UHFFFAOYSA-N

物化性质

• 沸点：
  398.8±34.0 °C(Predicted)
• 密度：
  1.359±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.42
• 重原子数：
  17.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  59.5
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  喹啉-6-基二甲基氨基磺酸酯 、 potassium tert-butyl butyl{(trifluoroborato)methyl}carbamate 在 chloro(2-dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]palladium(II) 、 potassium carbonate 作用下， 以 水 、 叔丁醇 为溶剂， 反应 18.0h， 以84%的产率得到tert-butyl butyl(quinolin-6-ylmethyl)carbamate
  参考文献：
  名称：

  Pd-Catalyzed Suzuki–Miyaura Cross-Coupling Reactions between Sulfamates and Potassium Boc-Protected Aminomethyltrifluoroborates

  摘要：

  Sulfamates were studied as the electrophilic partners in the palladium-catalyzed Suzuki-Miyaura cross-coupling reaction with potassium Boc-protected primary and secondary aminomethyltrifluoroborates. A broad range of substrates was successfully coupled to provide the desired products. Complex molecules containing a new carbon-carbon bond and an aminomethyl moiety could be prepared through this developed method.

  DOI：

  10.1021/ol401021x
• 作为产物：
  描述：

  6-羟基喹啉 、 二甲胺基磺酰氯 以 吡啶 为溶剂， 反应 22.0h， 以84%的产率得到喹啉-6-基二甲基氨基磺酸酯
  参考文献：
  名称：

  Suzuki−Miyaura Cross-Coupling of Aryl Carbamates and Sulfamates: Experimental and Computational Studies

  摘要：

  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.

  DOI：

  10.1021/ja200398c

文献信息

• Mechanistic Study of an Improved Ni Precatalyst for Suzuki–Miyaura Reactions of Aryl Sulfamates: Understanding the Role of Ni(I) Species
  作者：Megan Mohadjer Beromi、Ainara Nova、David Balcells、Ann M. Brasacchio、Gary W. Brudvig、Louise M. Guard、Nilay Hazari、David J. Vinyard

  DOI：10.1021/jacs.6b11412

  日期：2017.1.18

  function at room temperature. Mechanistic studies on precatalyst activation and the speciation of nickel during catalysis reveal that Ni(I) species are formed in the catalytic reaction via two different pathways: (i) the precatalyst (dppf)Ni(o-tolyl)(Cl) undergoes comproportionation with the active Ni(0) species; and (ii) the catalytic intermediate (dppf)Ni(Ar)(sulfamate) (Ar = aryl) undergoes comproportionation

  对于 Suzuki-Miyaura 偶联反应，镍预催化剂可能是传统钯预催化剂的更可持续的替代品。目前，Suzuki-Miyaura 偶联反应引起了人们极大的兴趣，该反应涉及容易获得的酚类衍生物，例如氨基磺酸芳基酯，因为氨基磺酸酯部分可以作为一个导向基团，用于在交叉偶联之前对亲电子试剂的芳香骨架进行预官能化。通过评估 Ni(0)、(I) 和 (II) 氧化态的配合物，我们报告了一种前催化剂，(dppf)Ni(o-tolyl)(Cl) (dppf = 1,1'-bis(diphenylphosphino)ferrocene )，对于涉及芳基氨基磺酸酯和硼酸的 Suzuki-Miyaura 偶联反应，与其他报道的系统相比，该反应在显着更低的催化剂负载和更温和的反应条件下运行。在某些情况下，它甚至可以在室温下工作。对催化剂前体活化和催化过程中镍形态形成的机理研究表明，Ni(I) 物种在催化反应中通过两种不同的途径形成：(i)
• Palladium-catalyzed Suzuki–Miyaura coupling of aryl sulfamates with arylboronic acids
  作者：Zhan-Yong Wang、Qin-Na Ma、Ren-Hao Li、Li-Xiong Shao

  DOI：10.1039/c3ob41382a

  日期：——

  showed efficient catalytic activity toward the Suzuki–Miyaura coupling of aryl sulfamates with arylboronic acids or potassium phenyltrifluoroborate, giving the expected coupling products in good to high yields. It should be noted that this is the first example so far of the phosphine-free, NHC–Pd(II) complexes catalyzed Suzuki–Miyaura coupling of aryl sulfamates with arylboronic acids.

  现成的NHC-Pd（II）-Mp配合物2对芳基氨基磺酸与芳基硼酸或苯基三氟硼酸钾的Suzuki-Miyaura偶联显示出有效的催化活性，从而以高至高收率提供了预期的偶联产物。应当指出，这是迄今为止不含膦的NHC-Pd（II）配合物催化氨基磺酸芳基磺酸盐与芳基硼酸的Suzuki-Miyaura偶联反应的第一个例子。