(R)-2-bis(3,5-bis(trifluoromethyl)phenyl)phosphinyl-1,1'-binaphthyl

• 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: (R)-2-bis(3,5-bis(trifluoromethyl)phenyl)phosphinyl-1,1'-binaphthyl
• 英文别名: 2-bis[3,5-bis(trifluoromethyl)phenyl]phosphoryl-1-naphthalen-1-ylnaphthalene
• 化学式: C₃₆H₁₉F₁₂OP
• 分子量: 726.501
• InChiKey: RQGLMQCCXIVYCN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.7
• 重原子数：
  50
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  (R)-2-bis(3,5-bis(trifluoromethyl)phenyl)phosphinyl-1,1'-binaphthyl 在 三氯硅烷 、 亚磷酸三乙酯 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 18.0h， 以88%的产率得到(S)-2-bis[3,5-bis(trifluoromethyl)phenyl]phosphino-1,1'-binaphthyl
  参考文献：
  名称：

  使用三苯膦或亚磷酸三乙酯作为氧受体，使膦氧化物的立体特异性脱氧并保持构型。

  摘要：

  [反应：见正文]描述了一种新的方案，用于在保持构型的情况下对各种氧化膦进行脱氧。新方法的优点包括条件更温和，反应时间大大缩短。还介绍了有关起始氧化膦与牺牲性三苯膦之间氧转移的机理的研究。

  DOI：

  10.1021/ol048227c
• 作为产物：
  描述：

  氯二[3,5-二(三氟甲基)苯基]膦 在 碘 、 氧气 、 magnesium 作用下， 以 四氢呋喃 、 甲苯 、 苯 为溶剂， 反应 5.0h， 生成 (R)-2-bis(3,5-bis(trifluoromethyl)phenyl)phosphinyl-1,1'-binaphthyl
  参考文献：
  名称：

  使用三苯膦或亚磷酸三乙酯作为氧受体，使膦氧化物的立体特异性脱氧并保持构型。

  摘要：

  [反应：见正文]描述了一种新的方案，用于在保持构型的情况下对各种氧化膦进行脱氧。新方法的优点包括条件更温和，反应时间大大缩短。还介绍了有关起始氧化膦与牺牲性三苯膦之间氧转移的机理的研究。

  DOI：

  10.1021/ol048227c

文献信息

• Modification of Chiral Monodentate Phosphine (MOP) Ligands for Palladium-Catalyzed Asymmetric Hydrosilylation of Styrenes
  作者：Tamio Hayashi、Seiji Hirate、Kenji Kitayama、Hayato Tsuji、Akira Torii、Yasuhiro Uozumi

  DOI：10.1246/cl.2000.1272

  日期：2000.11

  In the palladium-catalyzed asymmetric hydrosilylation of styrene with trichlorosilane, several chiral monophosphine ligands, (R)-2-diarylphosphino-1,1′-binaphthyls (2), were examined for their enantioselectivity. The highest enantioselectivity was observed in the reaction with (R)-2-bis[3,5-bis(trifluoromethyl)phenyl]phosphino-1,1′-binaphthyl (2g), which gave (S)-1-phenylethanol of 98% ee after oxidation of the hydrosilylation product.

  在钯催化的苯乙烯与三氯硅烷的不对称氢化硅烷化反应中，研究了几种手性单膦配体 (R)-2-二芳基膦基-1,1'-联萘 (2) 的对映选择性。在与 (R)-2-双[3,5-双(三氟甲基)苯基]膦基-1,1'-联萘 (2g) 的反应中观察到最高的对映选择性，得到 98 的 (S)-1-苯基乙醇氢化硅烷化产物氧化后的％ee。
• Asymmetric Hydrosilylation of Styrenes Catalyzed by Palladium−MOP Complexes:  Ligand Modification and Mechanistic Studies
  作者：Tamio Hayashi、Seiji Hirate、Kenji Kitayama、Hayato Tsuji、Akira Torii、Yasuhiro Uozumi

  DOI：10.1021/jo001614p

  日期：2001.2.1

  In the palladium-catalyzed asymmetric hydrosilylation of styrene (3a) with trichlorosilane, several chiral monophosphine ligands, (R)-2-diarylphosphino-1,1'-binaphthyls(2a-g), were examined for their enantioselectivity. The highest enantioselectivity was observed in the reaction with (R)-2-bis [3,5-bis(trifluoromethyl)phenyl] phosphino-l,1'-binaphthyl (2g), which gave (S)-1-phenylethanol (5a) of 98% ee after oxidation of the hydrosilylation product, 1-phenyl-1-(trichlorosilyl)ethane (4a). The palladium complex of 2g also efficiently catalyzed the asymmetric hydrosilylation of substituted styrenes on the phenyl ring or at the beta position to give the corresponding chiral benzylic alcohols of over 96% ee. Deuterium-labeling studies on the hydrosilylation of regiospecifically deuterated styrene revealed that P-hydrogen elimination from l-phenylethyl(silyl)palladium intermediate is very fast compared with reductive elimination giving hydrosilylation product when ligand 2g is used. The reaction of o-allylstyrene (9) with trichlorosilane catalyzed by (R)-2g/Pd gave (1S,2R)-1-methyl-2-(trichlorosilylmethyl)indan (10) (91% ee) and (S)-1-(2-(propenyl)phenyl)-1-trichlorosilylethanes (11a and 11b) (95% ee). On the basis of their opposite configurations at the benzylic position, a rationale for the high enantioselectivity of ligand 2g is proposed.
• Stereospecific Deoxygenation of Phosphine Oxides with Retention of Configuration Using Triphenylphosphine or Triethyl Phosphite as an Oxygen Acceptor
  作者：Hai-Chen Wu、Jin-Quan Yu、Jonathan B. Spencer

  DOI：10.1021/ol048227c

  日期：2004.12.1

  [reaction: see text] A new protocol for deoxygenation of various phosphine oxides with retention of configuration is described. The advantage of the new method includes milder conditions and considerably shortened reaction times. Mechanistic studies about the oxygen transfer between the starting phosphine oxide and the sacrificial triphenylphosphine are also presented.

  [反应：见正文]描述了一种新的方案，用于在保持构型的情况下对各种氧化膦进行脱氧。新方法的优点包括条件更温和，反应时间大大缩短。还介绍了有关起始氧化膦与牺牲性三苯膦之间氧转移的机理的研究。