(R)-phenyl-o-anisylphenylphosphinite | 1417912-03-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (R)-phenyl-o-anisylphenylphosphinite
• 英文别名: o-anisyl-phenyl-phenylphosphinite；(R)-(2-methoxyphenyl)-phenoxy-phenylphosphane
• CAS: 1417912-03-8
• 化学式: C₁₉H₁₇O₂P
• 分子量: 308.317
• InChiKey: NZEADMPAXHEODM-JOCHJYFZSA-N

物化性质

• 沸点：
  431.6±47.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R)-phenyl-o-anisylphenylphosphinite 、 2-bromophenyl phenyl sulfide 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.0h， 以39%的产率得到(2-methoxyphenyl)phenyl[2-(phenylthio)-phenyl]phosphine
  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：

  2-methoxyphenyllithium 在 三乙烯二胺 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 1.0h， 生成 (R)-phenyl-o-anisylphenylphosphinite
  参考文献：
  名称：

  使用P（III）-磷在两个P中心设计P致色性1,2-二膦基苯

  摘要：

  使用芳烃化学方法报道了一种在一个或两个磷中心具有手性的P-手性1,2-二膦基苯（DP * B）的新对映异构体合成。该原理基于1，2-二溴苯与仲磷硼烷的连续反应，然后由DABCO除去硼烷，最后与氯代膦酸酯或P（III）-色性次膦酸酯反应。通过（S，S）-1,2-双（邻-茴香基苯基膦基）苯的立体选择性制备证明了该合成的效率。报道了在不对称的Rh或Pd催化反应中DIPAMP和同手性DP * B配体的比较。

  DOI：

  10.1021/acs.orglett.6b01275

文献信息

• [EN] P-CHIROGENIC ORGANOPHOSPHORUS COMPOUNDS<br/>[FR] COMPOSÉS ORGANOPHOSPHOREUX P-CHIROGÈNES
  申请人：CENTRE NAT RECH SCIENT

  公开号：WO2013007724A1

  公开（公告）日：2013-01-17

  The present invention relates to novel P-chirogenic organophosphorus compounds of general formula (I). The present invention also provides a process for the synthesis of said compounds of formula (I). The present invention also relates to intermediate products of general formulae (II), (III) and (IV), as shown below, which are involved in the synthesis of compounds (I). Further, the invention relates to metal complexes comprising compounds (I) as ligands. The novel compounds and complexes of the present invention are useful in asymmetric catalysis by transition metal complexes or organocatalysis, especially for asymmetric hydrogenation or allylation. Compounds of general formula (I) may useful as agrochemical and therapeutic substances, or as reagents or intermediates for fine chemistry.

  本发明涉及一般式(I)的新型P-手性有机磷化合物。本发明还提供了一种合成上述一般式(I)化合物的方法。本发明还涉及一般式(II)、(III)和(IV)的中间产物，如下所示，这些中间产物参与了化合物(I)的合成。此外，本发明涉及包含化合物(I)作为配体的金属配合物。本发明的新型化合物和配合物在过渡金属配合物或有机催化剂的手性催化中具有用途，特别是在不对称氢化或烯丙基化中。一般式(I)的化合物可用作农药和治疗物质，或作为精细化学的试剂或中间体。
• P-CHIROGENIC ORGANOPHOSPHORUS COMPOUNDS
  申请人：CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE (CNRS)

  公开号：US20140142325A1

  公开（公告）日：2014-05-22

  Novel P-chirogenic organophosphorus compounds of general formula (I), a process for the synthesis of the compounds of formula (I), and intermediate products of general formulae (II), (III) and (IV), as shown below, are involved in the synthesis of compounds (I). Metal complexes including compounds (I) as ligands are also described. The novel compounds and complexes are useful in asymmetric catalysis by transition metal complexes or organocatalysis, especially for asymmetric hydrogenation or allylation. Compounds of general formula (I) may be useful as agrochemical and therapeutic substances, or as reagents or intermediates for fine chemistry.

  通式为（I）的新型P-手性有机磷化合物的合成方法，以及通式为（II）、（III）和（IV）的中间体，如下所示，参与了化合物（I）的合成。还描述了以化合物（I）为配体的金属配合物。这些新型化合物和配合物在过渡金属配合物或有机催化剂的不对称催化中非常有用，特别是在不对称氢化或烯丙基化中。通式为（I）的化合物可能在农药和治疗物质中有用，或作为精细化学的试剂或中间体。
• US9186661B2
  申请人：——

  公开号：US9186661B2

  公开（公告）日：2015-11-17
• US9707553B2
  申请人：——

  公开号：US9707553B2

  公开（公告）日：2017-07-18
• Designing P-Chirogenic 1,2-Diphosphinobenzenes at Both P-Centers Using P(III)-Phosphinites
  作者：Jérôme Bayardon、Yoann Rousselin、Sylvain Jugé

  DOI：10.1021/acs.orglett.6b01275

  日期：2016.6.17

  synthesis of P-chirogenic 1,2-diphosphinobenzenes (DP*B) bearing the chirality on one or both phosphorus centers is reported using aryne chemistry. The principle is based on successive reactions of 1,2-dibromobenzene with sec-phosphide boranes, then DABCO to remove the borane, and finally with chlorophosphines or P(III)-chirogenic phosphinites. The efficiency of this synthesis was demonstrated by the stereoselective

  使用芳烃化学方法报道了一种在一个或两个磷中心具有手性的P-手性1,2-二膦基苯（DP * B）的新对映异构体合成。该原理基于1，2-二溴苯与仲磷硼烷的连续反应，然后由DABCO除去硼烷，最后与氯代膦酸酯或P（III）-色性次膦酸酯反应。通过（S，S）-1,2-双（邻-茴香基苯基膦基）苯的立体选择性制备证明了该合成的效率。报道了在不对称的Rh或Pd催化反应中DIPAMP和同手性DP * B配体的比较。