N-((dimethyl(phenyl)silyl)(phenyl)methyl)-P,P-diphenylphosphinic amide | 850790-80-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: N-((dimethyl(phenyl)silyl)(phenyl)methyl)-P,P-diphenylphosphinic amide
• 英文别名: P,P-diphenyl-N-((dimethylphenylsilyl)(phenyl)methylyl)phosphinic amide；P,P-diphenyl-N-{[dimethyl(phenyl)silyl](phenyl)methyl}phosphinic amide；1-[dimethyl(phenyl)silyl]-N-diphenylphosphoryl-1-phenylmethanamine
• CAS: 850790-80-6
• 化学式: C₂₇H₂₈NOPSi
• 分子量: 441.585
• InChiKey: IQJJCKNADUOWAG-UHFFFAOYSA-N

物化性质

• 熔点：
  145 °C
• 沸点：
  571.8±60.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  31
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-((dimethyl(phenyl)silyl)(phenyl)methyl)-P,P-diphenylphosphinic amide 、 二碳酸二叔丁酯 在 盐酸 作用下， 以 四氢呋喃 、 水 为溶剂， 以82%的产率得到tert-butyl [dimethyl(phenyl)silyl](phenyl)methylcarbamate
  参考文献：
  名称：

  Stereoselective Synthesis of α-Silylamines by the Direct Addition of Silyl Anions to Activated Imines

  摘要：

  A highly efficient stereoselective synthesis of unusual alpha-silylamines via a direct silyl anion addition reaction is reported. This approach is convergent and avoids any problematic aza-Brook shifts of the anionic intermediates. The use of enantiopure tert-butanesulfinyl imines as the electrophiles affords exceedingly high levels of diastereocontrol for the newly formed stereogenic carbon.

  DOI：

  10.1021/ol050244u
• 作为产物：
  描述：

  二苯基磷酰胺 在 四氯化钛 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 2.33h， 生成 N-((dimethyl(phenyl)silyl)(phenyl)methyl)-P,P-diphenylphosphinic amide
  参考文献：
  名称：

  Stereoselective Synthesis of α-Silylamines by the Direct Addition of Silyl Anions to Activated Imines

  摘要：

  A highly efficient stereoselective synthesis of unusual alpha-silylamines via a direct silyl anion addition reaction is reported. This approach is convergent and avoids any problematic aza-Brook shifts of the anionic intermediates. The use of enantiopure tert-butanesulfinyl imines as the electrophiles affords exceedingly high levels of diastereocontrol for the newly formed stereogenic carbon.

  DOI：

  10.1021/ol050244u

文献信息

• Activation of the Si−B Linkage: Copper-Catalyzed Addition of Nucleophilic Silicon to Imines
  作者：Devendra J. Vyas、Roland Fröhlich、Martin Oestreich

  DOI：10.1021/ol200509c

  日期：2011.4.15

  quickly developed into a practical method to generate Cu−Si reagents. These silicon nucleophiles cleanly add to aldehyde-derived imine electrophiles to form α-silylated amines in protic media, and no carbon-to-nitrogen Brook-type rearrangement of the intermediate anion is observed. Aside from electron-withdrawing groups at the imine nitrogen atom, for example, SO2Tol and P(O)Ph2, previously delicate nitrogen

  通过铜催化的过渡金属化对Si-B键的激活迅速发展为一种生成Cu-Si试剂的实用方法。这些硅亲核试剂干净地添加到醛衍生的亚胺亲电试剂中，从而在质子介质中形成α-甲硅烷基化胺，并且未观察到中间阴离子的碳-氮布鲁克型重排。除了亚胺氮原子上的吸电子基团（例如SO 2 Tol和P（O）Ph 2）外，还可以耐受先前精密的氮取代基，例如苯基或二苯甲基。相同的协议还允许史无前例地添加代表酮的亚胺。
• Copper-Catalyzed Silylation of C(sp³)–H Bonds Adjacent to Amide Nitrogen Atoms
  作者：Jian-Jun Feng、Martin Oestreich

  DOI：10.1021/acs.orglett.8b01698

  日期：2018.7.20

  copper-catalyzed C–Si bond formation between N-halogenated amides and Si–B reagents is described. This oxidative coupling enables the silylation of C(sp3)–H bonds α to an amide nitrogen atom. The utility of the new method is demonstrated for sulfonamides, and N-chlorination with tBuOCl and C–H silylation employing CuSCN/4,4′-dimethoxy-2,2′-bipyridine as catalyst can be performed without purification of the

  描述了在N-卤代酰胺和Si-B试剂之间形成铜催化的C-Si键。这种氧化偶合使C（sp 3）–H键α与酰胺氮原子的甲硅烷基化。证明了该新方法对磺胺类药物的实用性，并且无需纯化N–即可进行以t BuOCl进行N-氯化和使用CuSCN / 4,4'-二甲氧基-2,2'-联吡啶作为催化剂进行C–H甲硅烷基化。 Cl中间体。
• Stereoselective Synthesis of α-Silylamines by the Direct Addition of Silyl Anions to Activated Imines
  作者：David M. Ballweg、Rebecca C. Miller、Danielle L. Gray、Karl A. Scheidt

  DOI：10.1021/ol050244u

  日期：2005.3.1

  A highly efficient stereoselective synthesis of unusual alpha-silylamines via a direct silyl anion addition reaction is reported. This approach is convergent and avoids any problematic aza-Brook shifts of the anionic intermediates. The use of enantiopure tert-butanesulfinyl imines as the electrophiles affords exceedingly high levels of diastereocontrol for the newly formed stereogenic carbon.