三(4-氟苯基)二氯化铋 | 118798-76-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 三(4-氟苯基)二氯化铋
• 英文名称: tris(4-fluorophenyl)bismuth dichloride
• CAS: 118798-76-8
• 化学式: C₁₈H₁₂BiCl₂F₃
• 分子量: 565.175
• InChiKey: ZKYFGDMNNNKBTN-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  4.0
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  三(4-氟苯基)二氯化铋 在 Crabtree's catalyst 、 (S)-2-甲基-CBS-恶唑硼烷 吡啶 、 4-二甲氨基吡啶 、 potassium fluoride 、 氢氧化钾 、 三丁基膦 、 偶氮二甲酸二异丙酯 、 dimethyl sulfide borane 、 氢气 、 双氧水 、 magnesium 、 N,N-二异丙基乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 乙二醇 、 N,N-二甲基甲酰胺 、 甲苯 、 叔丁醇 为溶剂， -50.0~100.0 ℃ 、101.33 kPa 条件下， 反应 86.34h， 生成 盐酸帕罗西汀
  参考文献：
  名称：

  Enantioselective total and formal syntheses of paroxetine (PAXIL) via phosphine-catalyzed enone α-arylation using arylbismuth(V) reagents: a regiochemical complement to Heck arylation

  摘要：

  Exposure of dihydropyridinone 1 to the arylbismuth(V) reagent (p-F-Ph)(3)BiCl2 in the presence of substoichiometric quantities of tributylphosphine (10 mol %) results in aryl transfer to the transiently generated (beta-phosphonio)enolate to provide the alpha-arylated enone 2. This transformation, which represents a regiochemical complement to the Mizoroki-Heck arylation, is used strategically in concise formal and enantioselective total syntheses of the blockbuster antidepressant (-)-paroxetine (PAXIL). (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.05.092
• 作为产物：
  描述：

  (对氟苯基)3Bi 在 Cl₂ 作用下， 以 氯仿 为溶剂， 以68%的产率得到三(4-氟苯基)二氯化铋
  参考文献：
  名称：

  Schmuck, Arno; Seppelt, Konrad, Chemische Berichte, 1989, vol. 122, p. 803 - 808

  摘要：

  DOI：

文献信息

• Multicomponent, Tandem 1,3- and 1,4-Bisarylation of Donor–Acceptor Cyclopropanes and Cyclobutanes with Electron-Rich Arenes and Hypervalent Arylbismuth Reagents
  作者：Biplab Mondal、Dinabandhu Das、Jaideep Saha

  DOI：10.1021/acs.orglett.0c01702

  日期：2020.7.2

  A tandem catalytic process for 1,3- and 1,4-bisarylation of donor–acceptor (D–A) cyclopropanes and cyclobutanes is disclosed. This strategy capitalizes on the use of two distinct sources of nucleophilic and electrophilic arylating agents, affording the formation of two new C–C bonds in an orchestrated multicomponent fashion with the aid of a catalytic Lewis acid. Mechanistic investigations have revealed

  公开了一种供体-受体（DA）环丙烷和环丁烷的1,3-和1,4-双芳基化的串联催化方法。该策略利用了亲核和亲电芳基化剂两个不同来源的使用，借助路易斯酸催化，以协调的多组分方式形成了两个新的C-C键。机理研究表明，这是一个立体选择过程，可以很容易地将产品精加工成其他有用的化合物。
• Phosphine Catalyzed α-Arylation of Enones and Enals Using Hypervalent Bismuth Reagents:  Regiospecific Enolate Arylation via Nucleophilic Catalysis
  作者：Phillip K. Koech、Michael J. Krische

  DOI：10.1021/ja048987i

  日期：2004.5.1

  Exposure of enones and enals to 20 mol % tributylphosphine in the presence of triarylbismuth(V) dichlorides results in regiospecific aryl transfer to the alpha-position of the enone or enal pronucleophile. These results represent the first examples of enolate arylation under the conditions of nucleophilic catalysis.
• Synthesis, halogenolysis, and crystal structure of hypervalent organobismuth compounds (10-Bi-5)
  作者：Xiang Chen、Keisuke Ohdoi、Yohsuke Yamamoto、Kinya Akiba

  DOI：10.1021/om00029a047

  日期：1993.5

  The stable 10-Bi-5 compounds (o-C6H4C(CF3)20)BiAr2R(3(Ar,R): 3a,p-CH3CrH4,p-CH3C6H4; 3b, P-CF3C6H4, p-CF3C6H4; 3c, p-FC6H4, p-FC6H4; 3d, p-CH3C6H4, p-CF3C6H4; 3e, p-CF3C6H4, p-CH3C6H4;3f,p-CH3Cr6H4,PhC=C;3g,p-CH3C6H4,Me) were synthesized. The X-ray structures of 3a,fg showed distorted-trigonal-bipyramidal geometries, and the electronegative apical PhC=C ligand of 3f made the apical Bi-O bond (2.243(3) angstrom) shorter than the Bi-O bond of 3a,g (2.323(4) angstrom in 3a and 2.328(7) angstrom in 3g). Halogenolysis of 3 with sulfuryl chloride or pyridinium bromide perbromide gave the five-coordinate bismuth compounds (o-C6H4C(CF3)20)BiArlAr2X (6 (Ar1, Ar2, X): 6a,p-CH3C6H4,p-CH3C6H4,Cl;6b,p-CF3C6H4,p-CF3C6H4,Cl;6c,p-FC6H4, p-FC6H4, Cl; 6d, p-CH3C6H4, p-CH3C6H4, Br; 6e, p-CH3C6H4, p-CF3C6H4, Cl; 6f, p-CH3C6H4, p-CF3C6H4, Br) in good to quantitative yield with apical covalent Bi-halogen bonds which were clearly shown by the X-ray analysis of 6a,b,d,e. The reactivity order of 3 for the halogenolysis was as follows: PhC=C-Bi > Me-Bi > p-CH3CrH4-Bi > p-CF3C6H4-Bi. Direct halogenolysis of the bismuth-carbon bond was suggested. The variable-temperature F-19 NMR of unsymmetrically substituted 6e,f did not show coalescence of the CF3 groups up to 170-degrees-C in a dilute solution of toluene-d8, and the energies of inversion at the bismuth atom should be higher than 21 kcal mol-1 at 170-degrees-C.