[Bis(dicyclohexylamino)phosphanyl](trimethylsilyl)diazomethane | 145397-27-9

• 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: [Bis(dicyclohexylamino)phosphanyl](trimethylsilyl)diazomethane
• 英文别名: N-cyclohexyl-N-[[diazo(trimethylsilyl)methyl]-(dicyclohexylamino)phosphanyl]cyclohexanamine
• CAS: 145397-27-9
• 化学式: C₂₈H₅₃N₄PSi
• 分子量: 504.815
• InChiKey: AEEXTVDWXIYSFH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.74
• 重原子数：
  34
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.96
• 拓扑面积：
  8.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  [Bis(dicyclohexylamino)phosphanyl](trimethylsilyl)diazomethane 以 正戊烷 为溶剂， 反应 36.0h， 以90%的产率得到[bis(dicyclohexylamino)phosphino](trimethylsilyl)carbene
  参考文献：
  名称：

  Synthesis and evolution of phosphanylcarbene–borane adducts

  摘要：

  双(二环己基氨基)膦酰基](三甲基硅基)重氮甲烷的光解作用会产生相应的稳定碳烯 1b，该碳烯 1b 与三乙基硼烷反应生成硼烷碳烯加合物 2b，在溶液中通过光谱测定其特征，然后重排和破碎成 P-二环己基氨基-C-(乙基)(三甲基硅基)膦烯 3b；三甲基硅基三氟甲磺酸加到 1b 中，得到亚甲基膦 4b。

  DOI：

  10.1039/c39930001354
• 作为产物：
  描述：

  lithio(trimethylsilyl)diazomethane 、 bis(dicyclohexylamino)chlorophosphane 以 四氢呋喃 为溶剂， 以85%的产率得到[Bis(dicyclohexylamino)phosphanyl](trimethylsilyl)diazomethane
  参考文献：
  名称：

  Sotiropoulos, J. M.; Baceiredo, A.; Bertrand, G., Bulletin de la Societe Chimique de France, 1992, # 4, p. 367 - 375

  摘要：

  DOI：

文献信息

• Stereoselectivity and Stereospecificity of Cyclopropanation Reactions with Stable (Phosphanyl)(silyl)carbenes
  作者：Stéphanie Goumri-Magnet、Tsuyoshi Kato、Heinz Gornitzka、Antoine Baceiredo、Guy Bertrand

  DOI：10.1021/ja994408b

  日期：2000.5.1

  The stable (phosphanyl)(silyl)carbenes 1a,b react efficiently with various electron-poor alkenes [methyl acrylate, 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene, styrene, (Z)- and (E)-2-deuteriostyrene, (E)-t-BuOC(O)CHCHC(O)OEt, and (E)-Me2NCOCHCHCO2Me] giving the corresponding cyclopropanes in good yields. The stereochemical outcome was such that all monosubstituted alkenes gave exclusively the syn isomer

  稳定的（膦基）（甲硅烷基）卡宾 1a、b 与各种缺电子烯烃 [丙烯酸甲酯、3,3,4,4,5,5,6,6,6-九氟己-1-烯，苯乙烯， (Z)- 和 (E)-2- 氘代苯乙烯、(E)-t-BuOC(O)CHCHC(O)OEt 和 (E)-Me2NCOCHCHCO2Me] 以良好的产率得到相应的环丙烷。立体化学结果是所有单取代烯烃都只给出顺式异构体（就磷酰基而言），而二取代烯烃的添加完全是立体有择的。观察到的高立体选择性归因于次级轨道相互作用（LUMOcarbene-HOMOalkene），类似于解释 Diels-Alder 反应中的内规则。
• The Stable (Phosphino)(Silyl)Carbene As A Useful Building Block: Synthesis And Reactivity of 2-Phosphorus-Substituted 2H-Azirines
  作者：Valérie Piquet、Antoine Baceiredo、Heinz Gornitzka、Françoise Dahan、Guy Bertrand

  DOI：10.1002/chem.19970031106

  日期：1997.11

  Abstract[Bis(dicyclohexylamino)phosphino]trimethylsilylcarbene (1) reacts with benzonitrile leading to the corresponding 2‐phosphino‐2H‐azirine 3 in 85% yield. Treatment of 3 with trifluoro‐methanesulfonic acid, methyl trifluoro‐methanesulfonate, or elemental sulfur leads to the P‐hydrogeno‐2‐phosphonio‐,P‐methyl‐2‐phosphonio‐, or 2‐thioxo‐phosphoranyl‐2H‐azirine (4, 5, and 7) in 77, 87, and 91% yields, respectively. Irradiation of 3 gives rise to the 1,2λ5‐azaphosphete 8 (98% yield). Treatment of 3 with BF3·OEt2, BH3·SMe2, Lawesson's reagent, or methyl isothiocyanate gives heterocycles 9 (90% yield), 10 (76% yield), 12 (83% yield), or 13 (80% yield), while under the same experimental conditions, heterocycle 8 reacts with the same reagents to give 9 (82% yield), 11 (83% yield), 12 (86% yield), and 15 (56% yield), respectively. Thermolysis of the P‐hydrogeno‐2‐phosphonio‐2H‐azirine 4 at 55°C leads to the cationic, four‐membered heterocycle 17 (96% yield), while photolysis of the P‐methylazirine analogue 5 in the presence of dimethyl acetylenedicarboxylate affords pyrrole 19 (64% yield). Irradiation of the thiox‐ophosphoranyl azirine 7 gives the 1,3,5λ5‐thiazaphosphole 20 in 79% yield. The influence of the coordination state of phosphorus on the reactivity of 2‐phosphorus‐substituted 2H‐azirines is studied.
• Romanenko, Vadim; Gudima, Andrei O.; Chernega, Alexandre N., Bulletin de la Societe Chimique de France, 1994, vol. 131, p. 748 - 753
  作者：Romanenko, Vadim、Gudima, Andrei O.、Chernega, Alexandre N.、Sotiropoulos, Jean-Marc、Alcaraz, Gilles、Bertrand, Guy

  DOI：——

  日期：——