(2,2-dimethyl-3H-1-benzofuran-7-yl) N,N-dimethylsulfamate | 1286762-99-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 香豆素
• 英文名称: (2,2-dimethyl-3H-1-benzofuran-7-yl) N,N-dimethylsulfamate
• CAS: 1286762-99-9
• 化学式: C₁₂H₁₇NO₄S
• 分子量: 271.337
• InChiKey: IRVSIAHVNJGHJR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  64.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2,2-dimethyl-3H-1-benzofuran-7-yl) N,N-dimethylsulfamate 在 potassium phosphate 、 Ni(PPh₃)₂(1-naphthyl)Cl 、 1-deuteriodiphenylmethanol 、 3-(2-isopropylphenyl)-4,5-dimethyl-1-(2,4,6-trimethylbenzyl)imidazolium chloride 作用下， 以 甲苯 为溶剂， 反应 15.0h， 以76%的产率得到C₁₀H₁₁⁽²⁾HO
  参考文献：
  名称：

  镍催化芳基氨基磺酸盐的脱氧氘化

  摘要：

  已开发了镍催化的芳基/杂芳基氨基磺酸盐的脱氧氘代反应，并以足够的催化效率和较高的氘代度将氘有效地掺入了多种芳族化合物中。该过程容许可还原的功能部分和杂环结构。另外，两次引入氘也成功地获得了具有高产率和氘含量的所需产物。

  DOI：

  10.1002/adsc.201601105
• 作为产物：
  描述：

  呋喃酚 、 二甲胺基磺酰氯 在 sodium hydride 作用下， 以 乙二醇二甲醚 为溶剂， 反应 17.0h， 以66%的产率得到(2,2-dimethyl-3H-1-benzofuran-7-yl) N,N-dimethylsulfamate
  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

• Nickel-Catalyzed Amination of Aryl Chlorides and Sulfamates in 2-Methyl-THF
  作者：Noah F. Fine Nathel、Junyong Kim、Liana Hie、Xingyu Jiang、Neil K. Garg

  DOI：10.1021/cs501045v

  日期：2014.9.5

  The nickel-catalyzed amination of aryl O-sulfamates and chlorides using the green solvent 2-methyl-THF is reported. This methodology employs the commercially available and air-stable precatalyst NiCl2(DME), is broad in scope, and provides access to aryl amines in synthetically useful yields. The utility of this methodology is underscored by examples of gram-scale couplings conducted with catalyst loadings

  报道了使用绿色溶剂2-甲基-THF的镍催化的芳基O-氨基磺酸盐和氯化物的胺化。该方法采用了可商购的且空气稳定的预催化剂NiCl2（DME），适用范围广，并提供了可用于合成的收率的芳基胺。该方法的实用性通过在催化剂负载量低至1 mol％镍的情况下进行的克级偶联的实例得到了强调。而且，所述的镍催化的胺化反应耐受杂环，并应证明可用于合成药物候选物和其他含杂原子的化合物。
• Nickel-Catalyzed Hydrodeoxygenation of Aryl Sulfamates with Alcohols as Mild Reducing Agents
  作者：Masami Kuriyama、Osamu Onomura、Kasumi Matsuo、Kosuke Yamamoto、Yosuke Demizu、Koyo Nishida

  DOI：10.1055/a-1548-8362

  日期：2021.12

  The nickel-catalyzed hydrodeoxygenation of aryl sulfamates has been developed with alcohols as mild reductants. A variety of functional groups and heterocycles were tolerated in this reaction system to give the desired products in high yields. In addition, the gram-scale process and stepwise cine-substitution were also achieved with high efficiency.

  使用醇作为温和的还原剂开发了镍催化的氨基磺酸芳基酯的加氢脱氧反应。在该反应体系中可以容忍多种官能团和杂环，从而以高产率得到所需的产物。此外，还高效地实现了克级工艺和逐步电影替代。
• Iron-Catalyzed Alkylations of Aryl Sulfamates and Carbamates
  作者：Amanda L. Silberstein、Stephen D. Ramgren、Neil K. Garg

  DOI：10.1021/ol301681z

  日期：2012.7.20

  The alkylation of aryl sulfamates and carbamates using iron catalysis is reported. The method constructs sp2–sp3 carbon–carbon bonds and provides synthetically useful yields across a range of substrates (>35 examples). The directing group ability of sulfamates and carbamates, accompanied by their low reactivity toward conventional cross-couplings, renders these substrates useful for the synthesis of

  报道了使用铁催化的芳基氨基磺酸酯和氨基甲酸酯的烷基化。该方法构建了 sp 2 –sp 3碳-碳键，并在一系列底物（> 35 个示例）中提供了合成有用的产率。氨基磺酸酯和氨基甲酸酯的导向基团能力，以及它们对传统交叉偶联的低反应性，使得这些底物可用于合成多官能化芳烃。
• Nickel-Catalyzed Suzuki–Miyaura Couplings in Green Solvents
  作者：Stephen D. Ramgren、Liana Hie、Yuxuan Ye、Neil K. Garg

  DOI：10.1021/ol401727y

  日期：2013.8.2

  The nickel-catalyzed Suzuki-Miyaura coupling of aryl halides and phenol-derived substrates with aryl boronic acids using green solvents, such as 2-Me-THF and tert-amyl alcohol, is reported. This methodology employs the commercially available and air-stable precatalyst, NiCl2(PCy3)(2), and gives biaryl products in synthetically useful to excellent yields. Using this protocol, bis(heterocyclic) frameworks can be assembled efficiently.
• Nickel-Catalyzed Suzuki-Miyaura Coupling in<i>t</i>-Amyl Alcohol for the Preparation of 5-(Furan-3-yl)pyrimidine
  作者：Liana Hie、Neil K. Garg

  DOI：10.1002/0471264229.os093.22

  日期：——