(S)-ferrocenyl[2-(bromomethyl)phenyl]phenylphosphine borane | 1453490-46-4

• 英文名称: (S)-ferrocenyl[2-(bromomethyl)phenyl]phenylphosphine borane
• CAS: 1453490-46-4
• 化学式: C₂₃H₂₃BBrFeP
• 分子量: 476.971
• InChiKey: CTIAQAWKBUXOKA-UHFFFAOYSA-N

物化性质

• 熔点：
  166-168 °C

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (S)-ferrocenyl[2-(bromomethyl)phenyl]phenylphosphine borane 、 甲基锂 以 四氢呋喃 、 正戊烷 为溶剂， 反应 1.5h， 以58%的产率得到
  参考文献：
  名称：

  P-chirogenic organocatalysts: application to the aza-Morita–Baylis–Hillman (aza-MBH) reaction of ketimines

  摘要：

  我们发现P-手性有机催化剂能够促进非环状α-酮酯衍生的酮亚胺的aza-Morita-Baylis-Hillman反应，实现高度的对映选择性。在P-手性有机催化的aza-MBH反应中，获得了高产率且高对映选择性的α,α-二取代α-氨基酸衍生物（最高可达97%对映体过量）。

  DOI：

  10.1039/c3cc44549f
• 作为产物：
  描述：

  (S)-ferrocenyl-(2-hydroxymethylphenyl)phenylphosphine-borane 在 sodium bromide 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 反应 3.0h， 以78%的产率得到(S)-ferrocenyl[2-(bromomethyl)phenyl]phenylphosphine borane
  参考文献：
  名称：

  Modular P-Chirogenic Phosphine-Sulfide Ligands: Clear Evidence for Both Electronic Effect and P-Chirality Driving Enantioselectivity in Palladium-Catalyzed Allylations

  摘要：

  Using the ephedrine methodology, modular stereo-selective syntheses of a new class of P-chirogenic phosphines bearing a sulfur-chelating arm (P*,S-hybrid ligand) are described. A first series of syntheses based on a Fries-like rearrangement of P-chirogenic phosphinite-boranes, which are prepared from 2-bromobenzyl or 2-bromophenethyl alcohol and are mediated by metal halide exchange, have been performed. This rearrangement affords phosphine-boranes stereospecifically with an o-hydroxy-alkylphenyl substituent. The latter residue is subsequently converted into a sulfur-containing group. In a second series, the stereoselective syntheses were achieved according to a new strategy involving a reaction of a thiophenyllithiurn reagent with a P-chirogenic phosphinite. The X-ray structures of the P*,S ligands and their palladium complexes allow us to address the absolute configuration at both the phosphorus and sulfur centers. The P*,S ligands were used in palladium-catalyzed allylic alkylations, as tests, affording asymmetric inductions up to 96% ee. Computer modeling corroborates the regio- and enantioselectivity of the Pd-catalyzed allylations and the low influence of the substituent carried by the sulfur moiety, particularly when the chelate forms a six-membered ring with the metal.

  DOI：

  10.1021/acs.organomet.5b00585