(S)-(-)-methyl-(2-bromophenyl)phenylphosphinite borane | 325153-77-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (S)-(-)-methyl-(2-bromophenyl)phenylphosphinite borane
• CAS: 325153-77-3
• 化学式: C₁₃H₁₅BBrOP
• 分子量: 308.95
• InChiKey: GBGRPUXVPRBMDN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.0
• 重原子数：
  17.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (S)-(-)-methyl-(2-bromophenyl)phenylphosphinite borane 在 叔丁基锂 、 sodium hydride 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 生成 (o-anisyl)(methyl)phenylphosphine borane
  参考文献：
  名称：

  Asymmetric synthesis of P-stereogenic o-hydroxyaryl-phosphine (borane) and phosphine-phosphinite ligands

  摘要：

  The first asymmetric synthesis of P-stereogenic 2-hydroxyarylphosphine ligands is described, using borane complexation methodology. This synthesis is based on the highly stereoselective preparation of bromoarylphosphinite boranes, leading to the 2-hydroxyarylphosphine derivatives, by an intramolecular ortho Fries-like rearrangement mediated in basic conditions. The o-anisyl-2-hydroxynaphthylphenylphosphine borane has been decomplexed in EtOH, affording the P(III)-stereogenic hydroxyarylphosphine ligand with 84% yield. The interest of the hydroxyarylphosphine borane is also demonstrated by the preparation of a new class of phosphine-phosphinite ligands, by trapping the rearrangement products first with chlorodiphenylphosphine, Ph2PCl, then with borane. The corresponding phosphine-phosphinites are obtained and purified as diborane complexes, with the decomplexation of these borane complexes being achieved by heating with dabco, to afford the free hybrid ligands with retention of the configuration at the P-atom (isolated yield up to 53%). (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00372-4
• 作为产物：
  描述：

  (S_p)-(+)-N-methyl-N-[(1S,2R)-(1-hydroxy-1-phenyl-prop-2-yl)]aminomethylphenylphosphine borane 在 盐酸 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 1.0h， 生成 (S)-(-)-methyl-(2-bromophenyl)phenylphosphinite borane
  参考文献：
  名称：

  Asymmetric synthesis of P-stereogenic o-hydroxyaryl-phosphine (borane) and phosphine-phosphinite ligands

  摘要：

  The first asymmetric synthesis of P-stereogenic 2-hydroxyarylphosphine ligands is described, using borane complexation methodology. This synthesis is based on the highly stereoselective preparation of bromoarylphosphinite boranes, leading to the 2-hydroxyarylphosphine derivatives, by an intramolecular ortho Fries-like rearrangement mediated in basic conditions. The o-anisyl-2-hydroxynaphthylphenylphosphine borane has been decomplexed in EtOH, affording the P(III)-stereogenic hydroxyarylphosphine ligand with 84% yield. The interest of the hydroxyarylphosphine borane is also demonstrated by the preparation of a new class of phosphine-phosphinite ligands, by trapping the rearrangement products first with chlorodiphenylphosphine, Ph2PCl, then with borane. The corresponding phosphine-phosphinites are obtained and purified as diborane complexes, with the decomplexation of these borane complexes being achieved by heating with dabco, to afford the free hybrid ligands with retention of the configuration at the P-atom (isolated yield up to 53%). (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00372-4