(R)-(-)-2-(diphenylphosphinyl)-1,1'-binaphthyl-2'-ol-N,N-dimethylthiocarbamate

• 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-(diphenylphosphinyl)-1,1'-binaphthyl-2'-ol-N,N-dimethylthiocarbamate
• 英文别名: O-[1-(2-diphenylphosphorylnaphthalen-1-yl)naphthalen-2-yl] N,N-dimethylcarbamothioate
• 化学式: C₃₅H₂₈NO₂PS
• 分子量: 557.653
• InChiKey: NXGYKVFSSVNNLK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.5
• 重原子数：
  40
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  61.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (R)-(-)-2-(diphenylphosphinyl)-1,1'-binaphthyl-2'-ol-N,N-dimethylthiocarbamate 在 lithium aluminium tetrahydride 、 三氯硅烷 、 potassium tert-butylate 、 三乙胺 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 xylene 为溶剂， 反应 12.15h， 生成 (R)-(+)-2-(diphenylphosphanyl)-2'-methylsulfanyl-1,1'-binaphthalenyl
  参考文献：
  名称：

  BINAPS - An axially chiral P,S-heterodonor ligand for asymmetric catalysis based on binaphthalene backbone

  摘要：

  含有螯合P、S-杂原子供体的配体2-二苯基膦基-1,1'-联萘-2'-硫醇（BINAPS）具有手性轴作为独特的立体发生元素，通过多步反应序列使用2,2'-二羟基-1,1'-联萘（BINOL）作为起始物质制备了其既对映的又无对映纯的形式。该反应序列完全保持立体构型，纯（S）-BINOL制备的（S）-11不会失去对映纯度。通过使用手性（S）-苄胺基Pd（II）-配合物19作为分离剂，可以通过分离法获得（R）-11。S-甲基或S-异丙基衍生物14已被用作手性配体，在Rh（I）催化的苯乙烯不对称氢甲酰化和乙酰苯酮的氢转移还原反应中取得了适度的成功（最高20% ee）。在适当的Pd-配合物存在下，相同的配体在苯乙烯的氢硅烷化（50% ee）和1,3-二苯基丙-2-烯基醋酸酯的烯基烷基化（60% ee）中提供更高的ee。关键词：杂原子供体配体、联萘衍生物、对映选择性催化、过渡金属催化剂、烯基烷基化。

  DOI：

  10.1139/v01-041
• 作为产物：
  描述：

  (R)-(+)-2-(diphenylphosphinyl)-2'-[(trifluoromethanesulfonyl)oxy]-1,1'-binaphthyl 在 sodium hydroxide 、 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 15.0h， 生成 (R)-(-)-2-(diphenylphosphinyl)-1,1'-binaphthyl-2'-ol-N,N-dimethylthiocarbamate
  参考文献：
  名称：

  Palladium-catalyzed asymmetric allylic substitutions by axially chiral P,S-, S,S-, and S,O-heterodonor ligands with a binaphthalene framework

  摘要：

  Axially chiral P,S-heterodonor ligand L1 is effective in the asymmetric allylic substitution of 1,3-diphenylpropenyl acetate with dimethyl malonate. its bidentate coordination pattern to a I'd metal center with both P and S atoms has been unambiguously established by X-ray diffraction and NMR spectroscopic analyses. Herein, we further disclose that axially chiral S,S-heterodonor ligands L2-L4 are also effective in the same reaction to give the allylic alkylation product in moderate to good ee. However, the corresponding S,O-heterodonor ligands are not as effective as the corresponding P,S- or S,S-heterodonor ligands in the same asymmetric reaction. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.08.008

文献信息

• BINAPS - An axially chiral <i>P</i>,<i>S</i>-heterodonor ligand for asymmetric catalysis based on binaphthalene backbone
  作者：Serafino Gladiali、Serenella Medici、Giovanna Pirri、Sonia Pulacchini、Davide Fabbri

  DOI：10.1139/v01-041

  日期：2001.5.1

  The chelating P,S-heterodonor ligand 2-diphenylphosphanyl-1,1'-binaphthalene-2'-thiol (11) (BINAPS), which features a chiral axis as the unique stereogenic element, has been prepared in both racemic and enantiopure form through a multistep reaction sequence using 2,2'-dihydroxy-1,1'-binaphthalene (BINOL) as the starting material. The reaction sequence is completely stereoconservative and (S)-11 is obtained with no loss of enantiopurity from pure (S)-BINOL. (R)-11 can be alternatively obtained by resolution of racemic 11 using the chiral (S)-benzylaminato Pd(II)-complex 19 as the resolving agent. The S-methyl or the S-i-propyl derivatives 14 have been used as chiral ligands in the Rh(I)-catalyzed asymmetric hydroformylation of styrene and in the hydrogen transfer reduction of acetophenone with modest success (up to 20% ee). In the presence of suitable Pd-complexes the same ligands provide higher ees in the hydrosilylation of styrene (50% ee) and in the allylic alkylation of 1,3-diphenylprop-2-enyl acetate (60% ee).Key words: heterodonor ligands, binaphthalene derivatives, enantioselective catalysis, transition metal catalysts, allylic alkylation.

  含有螯合P、S-杂原子供体的配体2-二苯基膦基-1,1'-联萘-2'-硫醇（BINAPS）具有手性轴作为独特的立体发生元素，通过多步反应序列使用2,2'-二羟基-1,1'-联萘（BINOL）作为起始物质制备了其既对映的又无对映纯的形式。该反应序列完全保持立体构型，纯（S）-BINOL制备的（S）-11不会失去对映纯度。通过使用手性（S）-苄胺基Pd（II）-配合物19作为分离剂，可以通过分离法获得（R）-11。S-甲基或S-异丙基衍生物14已被用作手性配体，在Rh（I）催化的苯乙烯不对称氢甲酰化和乙酰苯酮的氢转移还原反应中取得了适度的成功（最高20% ee）。在适当的Pd-配合物存在下，相同的配体在苯乙烯的氢硅烷化（50% ee）和1,3-二苯基丙-2-烯基醋酸酯的烯基烷基化（60% ee）中提供更高的ee。关键词：杂原子供体配体、联萘衍生物、对映选择性催化、过渡金属催化剂、烯基烷基化。
• Palladium-catalyzed asymmetric allylic substitutions by axially chiral P,S-, S,S-, and S,O-heterodonor ligands with a binaphthalene framework
  作者：Wen Zhang、Qin Xu、Min Shi

  DOI：10.1016/j.tetasy.2004.08.008

  日期：2004.10

  Axially chiral P,S-heterodonor ligand L1 is effective in the asymmetric allylic substitution of 1,3-diphenylpropenyl acetate with dimethyl malonate. its bidentate coordination pattern to a I'd metal center with both P and S atoms has been unambiguously established by X-ray diffraction and NMR spectroscopic analyses. Herein, we further disclose that axially chiral S,S-heterodonor ligands L2-L4 are also effective in the same reaction to give the allylic alkylation product in moderate to good ee. However, the corresponding S,O-heterodonor ligands are not as effective as the corresponding P,S- or S,S-heterodonor ligands in the same asymmetric reaction. (C) 2004 Elsevier Ltd. All rights reserved.
• Novel heterobidentate ligands for asymmetric catalysis: Synthesis and rhodium-catalysed reactions of S-alkyl (R)-2-diphenylphosphino-1,1′-binaphthyl-2′-thiol
  作者：Serafino Gladiali、Dore Antonio、Fabbri Davide

  DOI：10.1016/0957-4166(94)80141-x

  日期：1994.7

  Atropisomerically pure S-alkyl (R)-2-diphenylphosphino-1,1'-binaphthyl-2'-thiol derivatives have been synthesized through a multistep reaction sequence starting from (R)-binaphthol. Pd(II) and Rh(I) complexes containing the 3-methyl derivative 14 as a chelate ligand have been prepared and characterized. Rh(I) complexes containing 14 or the S-iso-propyl derivative 15 effectively catalyse the asymmetric hydroformylation of styrene and the hydrogen transfer reduction of acetophenone.
• Axially chiral P,S-heterodonor ligands with a binaphthalene framework for palladium-catalyzed asymmetric allylic substitutions: experimental investigation on the reversal of enantioselectivity between different alkyl groups on sulfur atom
  作者：Wen Zhang、Min Shi

  DOI：10.1016/j.tetasy.2004.09.027

  日期：2004.11

  The enantioselectivity in the palladium-catalyzed asymmetric allylic alkylation of 1,3-diphenylpropenyl acetate with dimethyl malonate using axially chiral P,S-heterodonor ligands BINAPS with different alkyl groups on sulfur atom has been investigated. Their bidentate coordination patterns to a Pd metal center with both P and S atoms have been unambiguously disclosed by X-ray diffraction. The reaction mechanism and the investigation on the reversal of enantioselectivity between different alkyl groups on sulfur atom have been discussed on the basis of the X-ray crystal structure and NMR spectroscopic data. (C) 2004 Elsevier Ltd. All rights reserved.