(R_P)-methyl(phenyl)(pyridin-2-ylmethyl)phosphine borane | 882535-75-3

• 英文名称: (R_P)-methyl(phenyl)(pyridin-2-ylmethyl)phosphine borane
• 英文别名: (S_P)-methyl(phenyl)(pyridin-2-ylmethyl)phosphine borane
• CAS: 882535-75-3；189273-74-3；1203661-40-8
• 化学式: C₁₃H₁₇BNP
• 分子量: 229.069
• InChiKey: DSNACFXCNBXENF-UHFFFAOYSA-N

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

• 作为产物：
  描述：

  碳酸甲丙酯 、 (R)-(+)-[(O-methyl)methylphenylphosphinite]borane 在 nBuLi 、 H₂O 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 以77%的产率得到(R_P)-methyl(phenyl)(pyridin-2-ylmethyl)phosphine borane
  参考文献：
  名称：

  Study of the Bonding Properties of the New Ligands C₅H₃N(2-R‘)(6-CH₂PPhR) toward Rhodium(I). Evidence for a Dynamic Competition for Bonding between O- and N-Donor Centers When R = o-Anisyl, R‘ = Me

  摘要：

  The bonding properties of the optically active chiral-at-P polydentate ligands C5H3N(2-R')(6-CH2PPhR) (R = Me, R' = H, Me; R o-anisyl, R' = H, Me) and the achiral ligand C5H3N(2-Me)(6-CH2PPh2) toward (COD)Rh+ are reported. The results show that steric hindrance of the 2-position of the pyridyl ring induces a labile character of the Rh-N bond. Moreover, for R = o-anisyl and R' = Me, a dynamic competition for bonding between the N-and O-donating centers is observed. Comparison of the solid state structures of complexes [Rh(COD)(C5H4N(2-CH2PPhMe)][BF4] and [Rh(COD)(C5H3N(2-Me)(6-CH2PPh2)][BF4] shows a significant bond lengthening of the Rh-N bond in the latter complex, consistent with its fluxional behavior observed in solution.

  DOI：

  10.1021/om960982+

文献信息

• Asymmetric Catalytic Synthesis of <i>P</i>-Stereogenic Phosphines via a Nucleophilic Ruthenium Phosphido Complex
  作者：Vincent S. Chan、Ian C. Stewart、Robert G. Bergman、F. Dean Toste

  DOI：10.1021/ja058100y

  日期：2006.3.1

  shown to be excellent nucleophiles, reacting via two-electron processes with a variety of electrophiles. A catalytic alkylation reaction was developed using an achiral ruthenium complex, which was then elaborated into a catalytic enantioselective synthesis of P-stereogenic phosphines. These useful and synthetically challenging phosphines can now be accessed in a single step from simple secondary phosphines

  磷化钌配合物已被证明是优异的亲核试剂，通过双电子过程与各种亲电子试剂反应。使用非手性钌络合物开发了催化烷基化反应，然后将其精心设计为对映选择性催化合成 P-立体膦。这些有用且合成上具有挑战性的膦现在可以从简单的仲膦和烷基卤化物通过一步获得。讨论了对映选择性烷基化的优化和范围。
• Chan, Vincent S.; Chiu, Melanie; Bergman, Robert G., Journal of the American Chemical Society, 2009, vol. 131, p. 6021 - 6032
  作者：Chan, Vincent S.、Chiu, Melanie、Bergman, Robert G.、Toste, F. Dean

  DOI：——

  日期：——
• The Hydroxyalkyl Moiety As a Protecting Group for the Stereospecific Alkylation of Masked Secondary Phosphine-Boranes
  作者：Sébastien Lemouzy、Marion Jean、Laurent Giordano、Damien Hérault、Gérard Buono

  DOI：10.1021/acs.orglett.5b03450

  日期：2016.1.4

  The synthesis of functionalized tertiary phosphine-boranes has been developed via a chemodivergent approach from readily accessible (hydroxymethyl) phosphine-boranes under mild conditions. O-Alkylation or decarbonylative P-alkylation product could be exclusively obtained. The P-alkylation reaction was found to proceed in moderate to very good yields and very high enantiospecificity (es >95%) using a variety of alkyl halides as electrophiles. The configurational stability of the sodium phosphido-borane intermediate was also investigated and allowed a deeper understanding of the reaction mechanism, furnishing secondary phosphine-boranes in moderate yield and enantiopurity.