(S)-ferrocenyl-(2-hydroxymethylphenyl)phenylphosphine-borane | 1429753-13-8

• 英文名称: (S)-ferrocenyl-(2-hydroxymethylphenyl)phenylphosphine-borane
• CAS: 1429753-13-8
• 化学式: C₂₃H₂₄BFeOP
• 分子量: 414.075
• InChiKey: HUIDXNMKVPYTAR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  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
• 作为产物：
  描述：

  (S)-ferrocenyl-(2-carboxylic-phenyl)phenylphosphine borane acid 在 dimethyl sulfide borane 作用下， 以 四氢呋喃 为溶剂， 以61%的产率得到(S)-ferrocenyl-(2-hydroxymethylphenyl)phenylphosphine-borane
  参考文献：
  名称：

  邻-（羟烷基）苯基对-发磷鎓盐作为功能性手性路易斯碱

  摘要：

  描述了带有邻羟基烷基螯合臂的P-手性膦的立体选择性合成。合成是基于对-手性的邻-溴苯基膦（硼烷）的羟烷基化或基于它们的碳酸化反应，然后进行还原。用苯甲醛或新戊醛进行的羟烷基化提供差向异构体的混合物，该差向异构体通过色谱法分离并通过其X射线结构表征。游离P-手性邻-（羟烷基）苯基膦的初步测定，作为催化的不对称aza-MBH反应中的新功能性Lewis碱，可产生ee值高达74％的β-氨基酯衍生物。

  DOI：

  10.1021/ol400515e

文献信息

• P-chirogenic organocatalysts: application to the aza-Morita–Baylis–Hillman (aza-MBH) reaction of ketimines
  作者：Shinobu Takizawa、Emmanuelle Rémond、Fernando Arteaga Arteaga、Yasushi Yoshida、Vellaisamy Sridharan、Jérôme Bayardon、Sylvain Jugé、Hiroaki Sasai

  DOI：10.1039/c3cc44549f

  日期：——

  The P-chirogenic organocatalysts were found to promote the enantioselective aza-Morita–Baylis–Hillman reaction of ketimines derived from acyclic α-keto esters. In the P-chirogenic organocatalyzed aza-MBH reactions, α,α-disubstituted α-amino acid derivatives were obtained in high yields with high enantioselectivities (up to 97% ee).

  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）。