(R)-(+)-2-(diphenylphosphinoyl)-2'-benzhydrylsulfanyl-1,1'-binaphthalenyl

• 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-(diphenylphosphinoyl)-2'-benzhydrylsulfanyl-1,1'-binaphthalenyl
• 英文别名: (R)-(+)-2-(diphenylphosphinyl)-2'-benzhydrylsulfanyl-1,1'-binaphthalenyl；1-(2-Benzhydrylsulfanylnaphthalen-1-yl)-2-diphenylphosphorylnaphthalene
• 化学式: C₄₅H₃₃OPS
• 分子量: 652.796
• InChiKey: OXGNIIREJZZNDR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.9
• 重原子数：
  48
• 可旋转键数：
  8
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.02
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R)-(+)-2-(diphenylphosphinoyl)-2'-benzhydrylsulfanyl-1,1'-binaphthalenyl 在 三氯硅烷 、 三乙胺 作用下， 以 甲苯 为溶剂， 反应 6.0h， 以39%的产率得到(R)-(+)-2-(diphenylphosphanyl)-2'-benzhydrylsulfanyl-1,1'-binaphthalenyl
  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
• 作为产物：
  描述：

  ((R)-2'-hydroxy-[1,1'-binaphthalen]-2-yl)diphenylphosphine oxide 在 lithium aluminium tetrahydride 、 sodium hydride 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 21.17h， 生成 (R)-(+)-2-(diphenylphosphinoyl)-2'-benzhydrylsulfanyl-1,1'-binaphthalenyl
  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

• 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.