(2'-methyl-[1,1'-biphenyl]-2-yl)diphenylphosphine oxide | 13175-77-4

• 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: (2'-methyl-[1,1'-biphenyl]-2-yl)diphenylphosphine oxide
• 英文别名: 2-diphenylphosphinyl-2'-methylbiphenyl；1-(2-Diphenylphosphorylphenyl)-2-methylbenzene
• CAS: 13175-77-4
• 化学式: C₂₅H₂₁OP
• 分子量: 368.415
• InChiKey: QMSQAQGSQATWAW-UHFFFAOYSA-N

物化性质

• 沸点：
  561.0±43.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  27
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.04
• 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：

  (2'-methyl-[1,1'-biphenyl]-2-yl)diphenylphosphine oxide 在 [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ 、 N-乙酰-Β-丙氨酸 、 三氯硅烷 、 cesium acetate 、 三乙胺 作用下， 以 甲苯 为溶剂， 反应 16.0h， 生成 (4''-methoxy-6'-methyl-[1,1':2',1''-terphenyl]-2-yl)diphenylphosphane
  参考文献：
  名称：

  钌催化的叔膦C–H芳基化

  摘要：

  设计了一种由钌（II）配合物催化的叔膦配体位点优先单CH芳基化的通用方案。该协议可以以中等到极好的收率获得一系列以克为单位的修饰的布赫瓦尔德-联芳基单膦。从通过ESI-MS观察到的中间体的知识中提出了催化循环。重要的是，这些单芳基化产物可以进一步转化为二苯并磷腈衍生物。

  DOI：

  10.1021/acs.orglett.9b00888
• 作为产物：
  描述：

  9,10-dihydro-9,9-diphenyl-9-phosphoniaphenanthrene bromide 在 sodium hydroxide 作用下， 生成 (2'-methyl-[1,1'-biphenyl]-2-yl)diphenylphosphine oxide
  参考文献：
  名称：

  磷杂环。第一部分共轭环状亚甲基磷烷

  摘要：

  环状季phospho盐9,10-二氢-9,9-二苯基-9-膦酰苯菲溴化物与氢氧化钠水溶液反应生成相应的环状亚甲基膦烷，其为不完全表征的橙色固体，与非环状相比，其相对水解的稳定性类似物，亚苄基三苯基磷烷，表明在含磷环中有一些芳香特性。

  DOI：

  10.1039/j39660002003

文献信息

• Palladium-catalyzed R2(O)P-directed C(sp2)-H activation
  作者：Hongyu Zhang、Shangdong Yang

  DOI：10.1007/s11426-015-5382-1

  日期：2015.8

  In recent years, transition-metal-catalyzed inert C-H bond activation has developed rapidly and is a powerful protocol for the construction of new C-C or C-X bonds and the introduction of new functional groups. Our group has also developed a series of R2(O)P-directed Pd-catalyzed C-H functionalizations involving olefination, hydroxylation, acetoxylation, arylation, and acylation through an uncommon seven-membered cyclo-palladium pretransition state. Unlike previously used directing groups, the R2(O)P group acts as a directing group and is also involved in the construction of P,-hetero-ligands.

  近年来，过渡金属催化的惰性C-H键活化发展迅速，是构建新的C-C或C-X键和引入新官能团的有力途径。我们课题组也发展了一系列R2(O)P导向的Pd催化C-H官能化反应，包括烯化、羟基化、醋酸化、芳基化和酰基化，通过一个罕见的七元环钯前过渡态。与先前使用的导向基团不同，R2(O)P基团既作为导向基团又参与构建P,-杂配体。
• Palladium-catalyzed R₂(O)P directed C(sp²)–H acetoxylation
  作者：Heng Zhang、Rong-Bin Hu、Xiao-Yu Zhang、Shi-Xia Li、Shang-Dong Yang

  DOI：10.1039/c4cc01238k

  日期：——

  A novel and efficient Pd-catalyzed C–H acetoxylation is described. The approach uses R₂(O)P as a directing group to synthesize various substituted 2′-phosphoryl biphenyl-2-OAc compounds.

  描述了一种新颖高效的钯催化的C-H乙酰化方法。该方法使用R₂(O)P作为导向基团，合成各种取代的2'-磷酸酯联苯-2-OAc化合物。
• Palladium-catalyzed P(O)R₂ directed C–H arylation to synthesize electron-rich polyaromatic monophosphorus ligands
  作者：Rong-Bin Hu、Heng Zhang、Xiao-Yu Zhang、Shang-Dong Yang

  DOI：10.1039/c3cc49050e

  日期：——

  Palladium-catalyzed arylation of (diisopropylphosphoryl)biphenyl skeleton derivatives by the P(O)R2 directed C-H functionalization was reported. The related products were obtained in high regioselectivity and good functional group tolerance was observed. This reaction provided a new and efficient pathway for the synthesis of polyaromatic monophosphorus ligands.

  报道了P（O）R2指导的CH官能团的钯催化的（二异丙基磷酰基）联苯骨架衍生物的芳基化。获得的相关产物具有较高的区域选择性，并且观察到良好的官能团耐受性。该反应为合成多芳族单磷配体提供了新的有效途径。
• P(O)R₂-Directed Enantioselective C–H Olefination toward Chiral Atropoisomeric Phosphine–Olefin Compounds
  作者：Shi-Xia Li、Yan-Na Ma、Shang-Dong Yang

  DOI：10.1021/acs.orglett.7b00608

  日期：2017.4.7

  An effective synthesis of chiral atropoisomeric biaryl phosphine-olefin compounds via palladium-catalyzed enantioselective C-H olefination has been developed for the first time. The reactions are operationally simple, tolerate wide functional groups, and have a good ee value, Notably, P(O)R-2 not only acts as the directing group to direct C-H activation in order to make a useful ligand but also serves to facilitate composition of the product in a useful manner in this transformation.
• Pd(II)-Catalyzed Ph₂(O)P-Directed C–H Olefination toward Phosphine–Alkene Ligands
  作者：Hong-Li Wang、Rong-Bin Hu、Heng Zhang、An-Xi Zhou、Shang-Dong Yang

  DOI：10.1021/ol402577p

  日期：2013.10.18

  The Pd(II)-catalyzed Ph-2(O)P-directed C-H olefination to synthesize alkene-phosphine compounds is reported. In contrast to previous examples of various directing groups that guide selective C-H activation, the Ph-2(O)P group not only acts as the directing group but also serves to construct the alkene-phosphine ligands. The monoprotected amino acid (MPAA) ligand Ac-Leu-OH is found to promote this reaction in a significant manner.