1-bromo-3-(4-[(tert-butyl)dimethylsilyloxy]but-1-ynyl)-5-(diphenylphosphanyl)benzene | 328917-32-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-bromo-3-(4-[(tert-butyl)dimethylsilyloxy]but-1-ynyl)-5-(diphenylphosphanyl)benzene
• 英文别名: 1-bromo-3-{4-[(tert-butyl)dimethylsilyloxy]but-1-ynyl}-5-(diphenylphosphanyl)benzene
• CAS: 328917-32-4
• 化学式: C₂₈H₃₂BrOPSi
• 分子量: 523.525
• InChiKey: ZLFHOIKITHHARF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.97
• 重原子数：
  32.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  1-bromo-3-(4-[(tert-butyl)dimethylsilyloxy]but-1-ynyl)-5-(diphenylphosphanyl)benzene 在 碘 正丁基锂 、 FeCl*H₂O 、 氧气 、 potassium thioacyanate 作用下， 以 四氢呋喃 、 甲苯 、 乙腈 为溶剂， 反应 4.25h， 生成 3-(4-[(tert-butyl)dimethylsilyloxy]but-1-ynyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl)phenyl(diphenyl)phosphane oxide
  参考文献：
  名称：

  Towards Asymmetric Catalysis in the Major Groove of 1,1′-Binaphthalenes

  摘要：

  Four new diphosphane ligands, (R)-4, (R)-5, (S)-6, and (R)-7 (Schemes 3, 4, 6, and 7), featuring metal-coordination sites located in the major groove of chiral 1,1'-binaphthalene clefts, were prepared in enantiomerically pure form. The performance of this new class of ligands was tested in enantioselective, Pd-catalyzed allylic alkylation reactions with acyclic and cyclic methyl carbonates 28-30 as substrates under various reaction conditions (Schemes 8 and 9). Using sodium phenyl sulfinate as a nucleophile, the reactivity of the catalysts formed with the new ligands and suitable palladium precursors was found satisfactory (> 90%); however, the ee values were in all cases poor (<4%). Slightly better results were obtained using anions of dimethyl malonate as nucleophiles, but, also in these cases, the ee values never exceeded 17% (Table). P-31-NMR-Spectroscopic investigations revealed the formation of multiple-catalyst species in solution (Fig. 2), and molecular modeling suggested a lack of embedding of the coordinated substrate in a 'chiral pocket' (Fig. 3), which probably accounts for the observed low level of enantioselectvity.

  DOI：

  10.1002/1522-2675(20001108)83:11<2865::aid-hlca2865>3.0.co;2-a
• 作为产物：
  描述：

  1,3,5-三溴苯 在 bis-triphenylphosphine-palladium(II) chloride 咪唑 、 copper(l) iodide 、 正丁基锂 、 三乙胺 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 20.5h， 生成 1-bromo-3-(4-[(tert-butyl)dimethylsilyloxy]but-1-ynyl)-5-(diphenylphosphanyl)benzene
  参考文献：
  名称：

  Towards Asymmetric Catalysis in the Major Groove of 1,1′-Binaphthalenes

  摘要：

  Four new diphosphane ligands, (R)-4, (R)-5, (S)-6, and (R)-7 (Schemes 3, 4, 6, and 7), featuring metal-coordination sites located in the major groove of chiral 1,1'-binaphthalene clefts, were prepared in enantiomerically pure form. The performance of this new class of ligands was tested in enantioselective, Pd-catalyzed allylic alkylation reactions with acyclic and cyclic methyl carbonates 28-30 as substrates under various reaction conditions (Schemes 8 and 9). Using sodium phenyl sulfinate as a nucleophile, the reactivity of the catalysts formed with the new ligands and suitable palladium precursors was found satisfactory (> 90%); however, the ee values were in all cases poor (<4%). Slightly better results were obtained using anions of dimethyl malonate as nucleophiles, but, also in these cases, the ee values never exceeded 17% (Table). P-31-NMR-Spectroscopic investigations revealed the formation of multiple-catalyst species in solution (Fig. 2), and molecular modeling suggested a lack of embedding of the coordinated substrate in a 'chiral pocket' (Fig. 3), which probably accounts for the observed low level of enantioselectvity.

  DOI：

  10.1002/1522-2675(20001108)83:11<2865::aid-hlca2865>3.0.co;2-a