(bis(diisopropylamino)phosphanyl)(trimethylsilyl)diazomethane | 97135-48-3

• 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(diisopropylamino)phosphanyl)(trimethylsilyl)diazomethane
• 英文别名: (trimethylsilyl)diazomethane；[Bis(diisopropylamino)phosphino](trimethylsilyl)-diazomethane；N-[[diazo(trimethylsilyl)methyl]-[di(propan-2-yl)amino]phosphanyl]-N-propan-2-ylpropan-2-amine
• CAS: 97135-48-3
• 化学式: C₁₆H₃₇N₄PSi
• 分子量: 344.556
• InChiKey: YUASZUIHRJMQJX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.04
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.94
• 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(diisopropylamino)phosphanyl)(trimethylsilyl)diazomethane 在 四氯化碳 作用下， 以 甲苯 、 苯 为溶剂， 反应 0.5h， 生成 4-[chloro-bis[di(propan-2-yl)amino]-λ5-phosphanylidene]thiadiazole-5-thione
  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：
• 作为产物：
  描述：

  C--N-(trimethylsilyl)nitrilimine 以60%的产率得到
  参考文献：
  名称：

  CASTAN, FLORENCE;BACEIREDO, ANTOINE;BIGG, DENNIS;BERTRAND, G., J. ORG. CHEM., 56,(1991) N, C. 1801-1807

  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。
• Phosphinocarbene-phosphaalkene rearrangement and intramolecular Wittig-like reaction involving a phosphorus vinyl ylide
  作者：Antoine. Baceiredo、Alain. Igau、Guy. Bertrand、Marie Joelle. Menu、Yves. Dartiguenave、Jean Jacques. Bonnet

  DOI：10.1021/ja00284a081

  日期：1986.11

  each isomer. Thus we have described a unique technique using peroxidase compound I for measuring rates and equilibria of keto-enol tautomerism which could readily be applied to a study of the influence of acid-base catalysts upon the rates. M-' s-l with a correction for hydrate formation.6

  表 I. 对于 2-甲基丙醛 K,,,, 是 1.7 X 和 kl 8.6 X 这些结果与通过其他实验和理论方法获得的结果相比2 丙醛和丁醛在其烯醇形式中都具有顺反异构体。我们的结果可以与突发阶段的单个指数曲线拟合，其后是线性零阶阶段。爆发结果表明两种几何异构体与化合物 I 的反应性没有可检测到的差异，这可能是因为已知化合物 I 反应缺乏选择性，或者一种异构体占主导地位。爆发后观察到的线性行为可能是两个零级反应的总和，每个异构体一个。因此，我们描述了一种使用过氧化物酶化合物 I 测量酮-烯醇互变异构的速率和平衡的独特技术，该技术可以很容易地应用于酸碱催化剂对速率影响的研究。M-' sl 修正了水合物的形成。 6
• Synthesis and reactivity of stable silyl-substituted nitrilimines
  作者：Florence Castan、Antoine Baceiredo、Dennis Bigg、G. Bertrand

  DOI：10.1021/jo00005a026

  日期：1991.3

  The reaction of chlorophosphanes and chlorosilanes with the lithium salts of the (bis(diisopropylamino)-thiophosphoranyl)-, bis(diisopropylamino)phosphanyl)-, (trimethylsilyl)-, and (triisopropylsilyl)diazomethane (1, 4, 5, 6) has been studied. Four isolable nitrilimines XCNNY (X = (iPr2N)2P(S), Y = SiiPr3, 10a; X = (iPr2N)2P, Y = SiPh3, 14a; X = (iPr2N)2P, Y = SiiPr3, 15a; X = Y = SiiPr3, 18a) and three observable nitrilimines (X = (iPr2N)2P(S), Y = SiMe3, 8a; X = (iPr2N)2P(S), Y = SiPh3, 9a; X = (iPr2N)2P, Y = SiMe3, 13a) have been obtained. The factors influencing the stability of nitrilimines are analyzed. Several examples of thermal nitrilimine-diazo rearrangements and photochemical nitrilimine-carbodiimide rearrangements are described. The regioselectivity of the reaction of the observable nitrilimines with methyl acrylate and methyl propiolate is compared to that reported for transient nitrilimines. An example of 1,3-addition of butyllithium to a nitrilimine is given.
• 1σ⁴,2σ<i>^x</i>-Diphosphetes (<i>x</i> = 2−6):  On the Persistence of the P−P Bond
  作者：Muriel Sanchez、Régis Réau、Heinz Gornitzka、Françoise Dahan、Manfred Regitz、Guy Bertrand

  DOI：10.1021/ja971821f

  日期：1997.10.1

  Irradiation of [bis(diisopropylamino)phosphino] (trimethylsilyl)diazomethane at 254 nm in the presence of tert-butylphosphaalkyne leads to 1 sigma(4),2 sigma(2)-diphosphete 1 in 90% yield. Derivative 1 reacts with Fe-2(CO)(9) and W(CO)(5)(THF) giving rise to the corresponding eta(1)-complexes 2 (48% yield) and 3 (75% yield), respectively. When 1 equiv of methyl trifluoromethanesulfonate and elemental selenium is added to derivative 1, the cationic and neutral 1 sigma(4),2 sigma(3)-diphosphetes 4 and 5 are isolated in 95 and 66% yields, respectively. Addition of 2 equiv of elemental selenium and bis(trimethylsilyl)peroxide to diphosphete 1 gave rise to 1 sigma(4),2 sigma(4)-diphosphetes 6 (43% yield) and 7 (84% yield), respectively. eta(1)-(1 sigma(4),2 sigma(2)-Diphosphete)tungsten complex 3 reacted with bis(trimethylsilyl)peroxide affording heterocyclic complex 8 (68% yield). Addition of 1 equiv of tetrachloro-o-benzoquinone (TCBQ) to the cationic 1 sigma(4),2 sigma(3)-diphosphete 4 and of 2 equiv to the 1 sigma(4),2 sigma(2)-diphosphete 1 affords the 1 sigma(4),2 sigma(5)- and 1 sigma(4),2 sigma(6)-diphosphetes 9 (86% yield) and 10 (92% yield), respectively. Addition of TCBQ to the eta(1)-(1 sigma(4),2 sigma(2)-diphosphete)tungsten complex 3 affords the eta(1)-(1 sigma(4),2 sigma(4)-diphosphete)complex 11 (88% yield), which reacts with 2 equiv of trimethylphosphine leading to the zwitterionic 1 sigma(4),2 sigma(3)-diphosphete 12 (46% yield). Cleavage of the Si-C bond of complex 3 with 1 equiv of tetrabutylammonium fluoride hydrate gives eta(1)-(1 sigma(4),2 sigma(2)-diphosphete)complex 13 (61% yield), which reacts with TCBQ leading to the cis-1,2-diphosphino alkene complex 14 (77% yield). These results demonstrate that the unsaturated four-membered ring skeleton is a remarkable template for inducing unusual P-P interactions. However, the presence of two very bulky substituents on the ethylenic moiety is necessary for the persistence of the cyclic structure, when the two phosphorus atoms feature a high coordination state. Single crystal X-ray diffraction studies of derivatives 7 and 11-14 have been carried out.
• Analogous .alpha.,.alpha.'-bis-carbenoid, triply bonded species: synthesis of a stable .lambda.3-phosphino carbene-.lambda.5-phosphaacetylene
  作者：Alain. Igau、Hansjorg. Grutzmacher、Antoine. Baceiredo、Guy. Bertrand

  DOI：10.1021/ja00227a028

  日期：1988.9