11-(dicyclohexylphosphinoyl)-12-phenyl-9,10-dihydro-9,10-ethenoanthracene | 1166994-74-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 11-(dicyclohexylphosphinoyl)-12-phenyl-9,10-dihydro-9,10-ethenoanthracene
• CAS: 1166994-74-6
• 化学式: C₃₄H₃₇OP
• 分子量: 492.641
• InChiKey: RTOGFBDAPZIZLZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.72
• 重原子数：
  36.0
• 可旋转键数：
  4.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  11-(dicyclohexylphosphinoyl)-12-phenyl-9,10-dihydro-9,10-ethenoanthracene 在 三氯硅烷 、 potassium selenocyanate 、 三乙胺 作用下， 以 甲醇 、 甲苯 为溶剂， 反应 40.25h， 生成
  参考文献：
  名称：

  Electron-Rich Trialkyl-Type Dihydro-KITPHOS Monophosphines: Efficient Ligands for Palladium-Catalyzed Suzuki–Miyaura Cross-Coupling. Comparison with Their Biaryl-Like KITPHOS Monophosphine Counterparts

  摘要：

  The Diels-Alder cycloaddition between dicyclohexylvinylphosphine oxide and anthracene or 9-methylanthracene affords the bulky electron-rich trialkyl-type dihydro-KITPHOS monophosphines 11-(dicyclohexylphosphinoyl)-12-phenyl-9,10-dihydro-9,10-ethenoanthracene and 11-(dicyclohexylphosphinoyl)-9-methyl-12-phenyl-9,10-dihydro-9,10-ethenoanthracene, respectively, after reduction of the corresponding oxide. Both phosphines are highly air-sensitive and rapidly oxidize on silica gel during purification but have been isolated as air-stable cyclometalated palladium precatalysts of the type [Pd{kappa(2)N2',C1-2-(2'-NH2C6H4)C6H4}Cl(L)]. Both palladium precatalysts form highly active systems for the Suzuki-Miyaura cross-coupling of a range of aryl chlorides with aryl boronic acids, giving the desired products in good to excellent yield under mild conditions and a catalyst loading of 0.25 mol %. A comparison of the performance of catalysts based on dihydro-KITPHOS monophosphines against their first-generation biaryl-like KITPHOS counterparts revealed that the latter are consistently more efficient for the vast majority of substrate combinations examined, albeit by only a relatively small margin in some cases. This, together with the greater air stability and ease of handling of biaryl-like KITPHOS monophosphines, renders them more practical ligands for palladium-based cross-coupling. The steric parameters of both classes of KITPHOS monophosphine and a selection of electron-rich biaryl monophosphines have been quantified using a combination of Solid-G to determine the percentage of the metal coordination sphere shielded by the phosphine (the G parameter), and Salerno molecular buried volume calculations (SambVca) to determine the percent buried volume (%V-bur); the corresponding Tolman cone angles have also been determined from correlations and the relative merits of the two approaches discussed. The electronic properties of these phosphines have also been investigated using DFT to calculate the A(1) nu(CO) frequency in LNi(CO)(3) (B3LYP/6-31G(2d,p)[LanL2DZ on Ni]), and the resulting computed electronic parameters (CEP) were used to estimate the corresponding experimental Tolman electronic parameters (TEP).

  DOI：

  10.1021/om3011992
• 作为产物：
  描述：

  蒽 、 (dicyclohexylphosphinoylethynyl)benzene 以80%的产率得到11-(dicyclohexylphosphinoyl)-12-phenyl-9,10-dihydro-9,10-ethenoanthracene
  参考文献：
  名称：

  通过1-炔基膦氧化物和蒽之间的[4 + 2]环加成反应，形成富含电子，双环的类似于芳基的KITPHOS单膦酸酯：高效配体，用于钯催化的CN和CC键形成

  摘要：

  富含电子的双环类芳基样KITPHOS单膦酸酯是通过Diels–Alder环加成反应在1-炔基膦氧化物和蒽之间以操作简单，高度模块化的合成方案制备的，该协议可允许使用结构上和电子上多样化的配体家族。这些配体的钯配合物是各种芳基氯化物的布赫瓦尔德-哈特维希胺化和铃木-宫浦偶合的高效催化剂，对于大多数底物组合，其性能均优于邻-（二环己基膦基）联苯。

  DOI：

  10.1002/adsc.200800307