[bis(dicyclohexylamino)phosphino](trimethylsilyl)carbene | 156280-08-9

• 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)phosphino](trimethylsilyl)carbene
• 英文别名: {bis(dicyclohexylamino)phosphanyl}(trimethylsilyl)carben；N-cyclohexyl-N-[(dicyclohexylamino)-(trimethylsilylmethylidyne)-lambda5-phosphanyl]cyclohexanamine；N-cyclohexyl-N-[(dicyclohexylamino)-(trimethylsilylmethylidyne)-λ5-phosphanyl]cyclohexanamine
• CAS: 156280-08-9
• 化学式: C₂₈H₅₃N₂PSi
• 分子量: 476.801
• InChiKey: KYTLFUXHBKZCSK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.07
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.96
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [bis(dicyclohexylamino)phosphino](trimethylsilyl)carbene 在 1,2,3,4,5,6,7,8-八硫杂环辛烷 、 silica gel 、 sulfur 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 33.0h， 生成
  参考文献：
  名称：

  The Stable (Phosphino)(Silyl)Carbene As A Useful Building Block: Synthesis And Reactivity of 2-Phosphorus-Substituted 2H-Azirines

  摘要：

  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.

  DOI：

  10.1002/chem.19970031106
• 作为产物：
  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

文献信息

• A Rare Example of a Rearrangement Involving Four Structural Isomers: -Phosphinonitrile/C-Phosphinoketenimine/1-Aza-4-phosphabutadiene/ 1,2-Dihydro-1,2-azaphosphete
  作者：Déborah Amsallem、Stéphane Mazières、Valérie Piquet-Fauré、Heinz Gornitzka、Antoine Baceiredo、Guy Bertrand

  DOI：10.1002/1521-3765(20021202)8:23<5305::aid-chem5305>3.0.co;2-6

  日期：2002.12.2

  )-carbene (1) reacts with dimethyl cyanamide to afford the original 1,2-dihydro-1,2-azaphosphete 4a (51% yield). The surprising formation of this heterocycle involves the transient formation of a nitrile, a keteneimine, and a 1-aza-4 lambda 3-phosphabutadiene derivative. By using substituent effects and different synthetic routes, all of these structural isomers have been isolated.

  稳定的化合物[双（二环己基氨基）膦基]（三甲基甲硅烷基）-卡宾（1）与二甲基氰胺反应，得到原始的1,2-二氢-1，2-氮杂磷4a（收率51％）。该杂环的惊人形成涉及腈，烯酮亚胺和1-氮杂-4λ3-磷丁二烯衍生物的瞬时形成。通过使用取代基效应和不同的合成途径，已分离了所有这些结构异构体。
• 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。
• Cowley, Alan H.; Gabbai, Francois P.; Carrano, Carlo J., Angewandte Chemie, 1994, vol. 106, p. 584 - 586
  作者：Cowley, Alan H.、Gabbai, Francois P.、Carrano, Carlo J.、Mokry, Ladd M.、Bond, Marcus R.、Bertrand, Guy

  DOI：——

  日期：——
• The Electrophilic Behavior of Stable Phosphanylcarbenes Towards Phosphorus Lone Pairs
  作者：Stéphanie Goumri-Magnet、Orest Polishchuk、Heinz Gornitzka、Colin J. Marsden、Antoine Baceiredo、Guy Bertrand

  DOI：10.1002/(sici)1521-3773(19991216)38:24<3727::aid-anie3727>3.3.co;2-1

  日期：1999.12.16
• 4-π-Electron 4-Membered Phosphorus Heterocycles
  作者：Regis Reau、Antoine Baceiredo、Guy Bertrand

  DOI：10.1080/10426509608545182

  日期：1996.1