1-benzothiepin-4-one | 65039-90-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并硫平类
• 英文名称: 1-benzothiepin-4-one
• 英文别名: 2,3-Dihydro-1-benzothiepin-4(5H)-on；3,5-dihydro-2H-benzo[b]thiepin-4-one；2,3-Dihydro-1-benzothiepin-4(5H)-one；3,5-dihydro-2H-1-benzothiepin-4-one
• CAS: 65039-90-9
• 化学式: C₁₀H₁₀OS
• 分子量: 178.255
• InChiKey: RMKIJTZGUNUYHT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-benzothiepin-4-one 以33%的产率得到
  参考文献：
  名称：

  PELLICCIARI R.; NATALINI B., J. CHEM. SOC. PERKIN TRANS., PART 1 , 1977, NO 16, 1822-1824

  摘要：

  DOI：
• 作为产物：
  描述：

  (but-3-yn-1-ylsulfinyl)benzene 在 silver hexafluoroantimonate 作用下， 以 二氯甲烷 为溶剂， 以94%的产率得到1-benzothiepin-4-one
  参考文献：
  名称：

  金(I)配合物催化炔基亚砜的重排

  摘要：

  报道了一系列金 (I) 催化的炔基亚砜重排反应。高炔丙基亚砜重排为苯并噻吩酮或苯并噻吩，而α-硫烯酮在炔丙基亚砜的反应中形成。所提出的机制是通过金促进的氧原子从亚砜转移到炔烃形成的 α-羰基金-类胡萝卜素中间体进行的。

  DOI：

  10.1021/ja070789e

文献信息

• [3,3]-Sigmatropic Rearrangement versus Carbene Formation in Gold-Catalyzed Transformations of Alkynyl Aryl Sulfoxides: Mechanistic Studies and Expanded Reaction Scope
  作者：Biao Lu、Yuxue Li、Youliang Wang、Donald H. Aue、Yingdong Luo、Liming Zhang

  DOI：10.1021/ja401343p

  日期：2013.6.12

  highly unlikely. Instead, a [3,3]-sigmatropic rearrangement of the initial cyclization intermediate offers a reaction path that can readily explain the high reaction efficiency and the lack of sulfonium formation. With internal alkyne substrates, however, the generation of a gold carbene species becomes competitive with the [3,3]-sigmatropic rearrangement. This reactive intermediate, nevertheless, does

  以芳基亚磺酰基为束缚氧化剂的末端炔烃的金催化分子内氧化是金化学中具有重大影响的反应，因为它向该领域引入了通过炔氧化生成金卡宾的高度有价值的概念。然而，α-氧代金卡宾在这些反应中的中介作用从未得到证实。详细的实验研究表明，此类反应性中间体参与二氢苯并硫杂环己烷的形成的可能性极小。相反，初始环化中间体的[3,3]-σ重排提供了一条反应路径，可以很容易地解释高反应效率和缺乏锍形成。然而，对于内部炔烃底物，金卡宾物质的生成变得与[3,3]-σ重排竞争。然而，这种反应性中间体不会继续提供弗里德尔-克拉夫茨型环化产物。广泛的密度泛函理论研究支持了这样的机制结论：环化产物是通过分子内[3,3]-σ重排形成的，而不是之前提出的弗里德尔-克拉夫茨型环化。凭借新的机理见解，这种多功能形成的中型含硫环烯酮的产品范围已轻松扩展到各种二氢苯并硫辛酮、四氢苯并环壬酮，甚至那些没有稠合苯环的化合物。除了金之外，Hg(OTf)2
• A DFT study on the formation of heterocycles <i>via</i> iodine(<scp>iii</scp>)-promoted ring expansion reactions
  作者：Natália Lussari、Ajmir Khan、Ronaldo A. Pilli、Alcindo A. Dos Santos、Luiz F. Silva、Ataualpa A. C. Braga

  DOI：10.1039/d2nj04393a

  日期：——

  The ring expansion of bicyclic heterocycles bearing an exocyclic double bond promoted by Koser's reagent [hydroxy(tosyloxy)iodobenzene, HTIB] is a mild, practical, and metal-free methodology to access seven-membered rings containing fused furan, indole, pyrrole, and thiophene heterocycles providing an entry to structurally challenging bioactive natural products as well as pharmaceuticals. Here we describe

  由 Koser 试剂 [羟基（甲苯磺酰氧基）碘苯，HTIB] 促进的带有环外双键的双环杂环的扩环是一种温和、实用且无金属的方法，可用于获得包含稠合呋喃、吲哚、吡咯和噻吩杂环为结构具有挑战性的生物活性天然产物和药物提供了一个入口。在这里，我们描述了在甲醇水溶液 (95 : 5 v/v) 中进行的反应的 DFT 结果。
• Exploring the Scope of Nitrogen Acyclic Carbenes (NACs) in Gold-Catalyzed Reactions
  作者：Camino Bartolomé、Domingo García-Cuadrado、Zoraida Ramiro、Pablo Espinet

  DOI：10.1021/om100507r

  日期：2010.8.23

  The catalytic activity of the recently reported nitrogen acyclic carbene (NAG) complexes of gold(I) has been investigated and compared with the reported activity of other gold(I) and gold(III) complexes. The complexes studied, [AuClC(NEt2)(NHTol-p)}], [AuClC(NEt2)(NHXylyl)}], and [Au(NTf2)C(NEt2)(NHXylyl)}], are very active in processes such as the rearrangement of homo-propargylsulfoxides, the intramolecular hydroamination of N-allenyl carbamates, the intramolecular hydroalkoxylation of allenes, the hydroarylation of acetylenecarboxylic acid ester, and the benzylation of anisole. Although the NAG ligands have not been optimized for the reactions tested, the yields obtained are usually similar and sometimes better than those reported with other catalysts, showing that the presence of N-H bonds and the wider N-C-N angle in the NAG (as compared to the NHC) complexes are not detrimental for the catalysis. For the hydroarylation reaction (where two competing products can be formed), the NAG complexes allow favoring one over the other. For the benzylation of anisole the selectivity is complementary to that obtained using H[AuCl4] as catalyst, and depending on the substrate, the NAG gold(III) complexes outperform the activity of H[AuCl4]. On average, the reactivity found suggests that the basicity of NACs toward gold(I) is very similar to that of NHCs and higher than that of phosphines.
• Gold-Catalyzed Intramolecular Redox Reaction of Sulfinyl Alkynes: Efficient Generation of α-Oxo Gold Carbenoids and Application in Insertion into RCO Bonds
  作者：Guotao Li、Liming Zhang

  DOI：10.1002/anie.200701449

  日期：2007.7.2
• Ricci,A. et al., Journal of Heterocyclic Chemistry, 1978, vol. 15, p. 927 - 928
  作者：Ricci,A. et al.

  DOI：——

  日期：——