(dicyclohexylphosphinoylethynyl)benzene | 1166994-71-3

• 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: (dicyclohexylphosphinoylethynyl)benzene
• 英文别名: dicyclohexyl(phenylethynyl)phosphine oxide；2-Dicyclohexylphosphorylethynylbenzene
• CAS: 1166994-71-3
• 化学式: C₂₀H₂₇OP
• 分子量: 314.408
• InChiKey: WUOJAZUOVLQATB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (dicyclohexylphosphinoylethynyl)benzene 在 三氯硅烷 、 三乙胺 作用下， 以 二氯甲烷 、 丙酮 、 甲苯 为溶剂， 反应 90.0h， 生成 [Pd{κ²N2′,C1-2-(2′-NH₂C₆H₄)C₆H₄}Cl{11-(dicyclohexylphosphino)-9-methyl-12-phenyl-9,10-dihydro-9,10-ethenoanthracene}]
  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：

  dicyclohexyl(phenylethynyl)phosphine 在 双氧水 作用下， 以 四氢呋喃 、 水 为溶剂， 以1.20 g的产率得到(dicyclohexylphosphinoylethynyl)benzene
  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

文献信息

• Synthesis of 3-Arylbenzofuran-2-ylphosphines via Rhodium-Catalyzed Redox-Neutral C–H Activation and Their Applications in Palladium-Catalyzed Cross-Coupling of Aryl Chlorides
  作者：Huanan Wang、Baiquan Wang、Bin Li

  DOI：10.1021/acs.joc.7b01566

  日期：2017.9.15

  regioselectivity with a broad substrate scope. The application of the resulting air-stable trivalent-phosphine containing dicyclohexylphosphino moiety in palladium-catalyzed Suzuki–Miyaura coupling and Buchwald–Hartwig amination of aryl chlorides is also described.

  通过[Cp * Rh（III）]催化N-苯氧基乙酰胺与1-炔基膦硫化物和氧化物的氧化还原-中性环化反应，然后还原，合成了一类新的芳基-杂芳基膦，即3-芳基苯并呋喃-2-基膦。这种经济的步伐反应在广泛的底物范围内以极好的区域选择性进行。还描述了所得的含空气稳定的三价膦二环己基膦基部分在钯催化的Suzuki-Miyaura偶联和芳基氯化物的Buchwald-Hartwig胺化中的应用。
• [EN] BICYCLIC MONOPHOSPHINES<br/>[FR] MONOPHOSPHINES BICYCLIQUES
  申请人：UNIV NEWCASTLE

  公开号：WO2009138708A1

  公开（公告）日：2009-11-19

  A compound of formula (I): wherein: RP1 and RP2 are independently selected from C3-12 alkyl groups; RC is a C5-6 aryl group, optionally substituted by one or more groups selected from: C1-7 alkyl, C1-7 alkoxy, halo, NH2, C1-7alkylamino, di-C1-7alkylamino, and C5-6 aryl; RA1 and RA2 are independently selected from H, Cl, and an optionally substituted group selected from: C1-7 alkyl, C1-7 alkoxy, C1-7 alkylthio and C5-6 aryl, wherein the optional substituents are selected from: C1-7 alkyl, C1-7 alkoxy, halo, NH2, C1-7alkylamino, di-C1-7alkylamino, and C5-6 aryl.

  式（I）的化合物：其中：RP1和RP2分别选自C3-12烷基基团；RC是C5-6芳基基团，可选择地被来自以下一种或多种基团的取代：C1-7烷基，C1-7烷氧基，卤素，NH2，C1-7烷基氨基，二C1-7烷基氨基和C5-6芳基；RA1和RA2分别选自H，Cl和可选择地被来自以下一种或多种基团的取代：C1-7烷基，C1-7烷氧基，C1-7烷硫基和C5-6芳基，其中可选择的取代基团选自：C1-7烷基，C1-7烷氧基，卤素，NH2，C1-7烷基氨基，二C1-7烷基氨基和C5-6芳基。
• Palladium-catalyzed dehydrogenative coupling of terminal alkynes with secondary phosphine oxides
  作者：Jia Yang、Tieqiao Chen、Yongbo Zhou、Shuangfeng Yin、Li-Biao Han

  DOI：10.1039/c4cc09567g

  日期：——

  The dehydrogenative coupling of terminal alkynes with secondary phosphine oxides is developed. In the presence of a silver additive, palladium acetate could efficiently catalyze the dehydrocoupling of secondary phosphine oxides with a variety of terminal alkynes to produce the corresponding alkynylphosphine oxides in high yields. A reaction mechanism is proposed.

  建立了末端炔烃与仲氧化膦的脱氢偶联反应。在存在银添加剂的情况下，乙酸钯可以有效地催化仲膦氧化物与各种末端炔烃的脱氢偶联，从而以高收率生产相应的炔基膦氧化物。提出了一种反应机理。
• Room-Temperature Alkynylation of Phosphine Oxides with Copper Acetylides: Practical Synthesis of Alkynylphosphine Oxides
  作者：Phidéline Gérard、Romain Veillard、Carole Alayrac、Annie-Claude Gaumont、Gwilherm Evano

  DOI：10.1002/ejoc.201501440

  日期：2016.2

  the synthesis of alkynylphosphine oxides based on the oxidative alkynylation of secondary phosphine oxides with copper acetylides was developed. Activation with molecular oxygen in the presence of either a mixture of 1,2-dimethylimidazole and triethylamine or N-methylimidazole alone enabled the formal umpolung of the poorly nucleophilic copper acetylides, which were coupled with phosphine oxides under

  开发了一种基于仲氧化膦与乙炔铜的氧化炔基化合成炔基氧化膦的有效方法。在 1,2-二甲基咪唑和三乙胺的混合物或单独的 N-甲基咪唑存在下，用分子氧活化能够使亲核性差的铜炔化物在非常温和的条件下与氧化膦偶联。该过程的显着特点是起始材料的可用性、用户友好性和温和的条件，允许合成复杂的炔基氧化膦。
• Electron-Rich Trialkyl-Type Dihydro-KITPHOS Monophosphines: Efficient Ligands for Palladium-Catalyzed Suzuki–Miyaura Cross-Coupling. Comparison with Their Biaryl-Like KITPHOS Monophosphine Counterparts
  作者：Simon Doherty、Julian G. Knight、Nicholas A. B. Ward、Dror M. Bittner、Corinne Wills、William McFarlane、William Clegg、Ross W. Harrington

  DOI：10.1021/om3011992

  日期：2013.3.25

  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 [Pdkappa(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).