N-tert-butyl-1,1-diphenylphosphinamine | 41979-47-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-tert-butyl-1,1-diphenylphosphinamine
• 英文别名: N-tert-butyl-1,1-diphenylphosphanamine；tert-Butylamino-diphenyl-phosphin；diphenylphosphino-t-butylamine；n-Tert-butyl-p,p-diphenylphosphinous amide；N-diphenylphosphanyl-2-methylpropan-2-amine
• CAS: 41979-47-9
• 化学式: C₁₆H₂₀NP
• 分子量: 257.315
• InChiKey: SYLDOBJLWJSZBQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-tert-butyl-1,1-diphenylphosphinamine 在 sodium hydride 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 2.0h， 生成 N-benzyl-N-(tert-butyl)diphenylphosphinamide
  参考文献：
  名称：

  Regio- and Diastereoselective Preparation of Tetrahydrobenzo[c]-1-aza-2λ⁵-phospholes through Dearomatization Cyclization of Lithiated N-Benzyl-N-alkyl(diphenyl)phosphinamides. Synthesis of γ-(N-Alkylamino)phosphinic Acids

  摘要：

  A study of the protonation of the cycloadducts derived from the dearomatization reaction of lithiated N-alkyl-N-benzyldiphenylphosphinamides has been carried out. The regio- and stereoselectivity of the process has been analyzed in terms of the size of the N-alkyl substituent, the acidity and size of the protonating reagent, and the cosolvent used. The optimization of these variables allowed the preparation of tetrahydrobenzo[c]-1-aza-2lambda(5)-phospholes containing a 1,3-cyclohexadiene or 1,4-cyclohexadiene system with moderate to excellent regio- and stereocontrol. The heterocycles were readily hydrolyzed, affording gamma-(N-alkylamino)diphenylphosphinic acids with the functionalities linked to a cyclohexadiene substructure.

  DOI：

  10.1021/jo025587+
• 作为产物：
  描述：

  二苯基氯化膦 、 叔丁胺 以 正己烷 为溶剂， 反应 12.0h， 生成 N-tert-butyl-1,1-diphenylphosphinamine
  参考文献：
  名称：

  氨基二苯基膦：同位素引起的化学位移 1Δ14/15N(31P)、偶联常数 1J(31P,15N) 以及化学位移 δ15N 和 δ31P

  摘要：

  一系列氨基二苯基膦 1 [Ph2P-N(H)tBu (a), -NEt2 (b), -NiPr2 (c)], 2 [Ph2P-NHPh (a), -NH-2-吡啶 (b), - NH-3-吡啶 (c), -NH-4-吡啶 (d), NH-嘧啶 (e), NH-2,6-Me2-C6H3 (f), NH-3-Me-2-吡啶 (g )], 3 [Ph2P-N(Me)Ph (a), -NPh2 (b)] 和 N-吡咯基二苯基膦 4 (Ph2P-NC4H4) 的制备和 NMR (1H, 13C, 31P, 15N NMR) 光谱研究. 同位素诱导的化学位移 1Δ14/15N(31P) 通过使用 HEED INEPT 实验在 15N 的天然丰度下确定。发现 1Δ14/15N(31P) 依赖于氮上的取代基（烷基 < H < 芳基；负值越来越大）。耦合常数 1J(31P,15N)（正号）的大小和符号由磷原

  DOI：

  10.1002/hc.1083

文献信息

• (N-lithioamino)diorganophosphanes and Bis(N-Lithioamino)organophosphanes: Synthesis and Structures
  作者：Bettina Eichhorn、Heinrich Nöth、Thomas Seifert

  DOI：10.1002/(sici)1099-0682(199912)1999:12<2355::aid-ejic2355>3.0.co;2-h

  日期：1999.12

  [PhP(NLiPh)2]2. Reaction of nBuLi with MeP(NHiPr)2 in hexane/THF leads to [MePN(Li)iPr]2·THF}4 with an asymmetric cluster structure comprising one LiP3, three LiPN2, three LiP2N and one LiN3 cluster units. The molecular structures of these compounds as determined by X-ray structure analysis show that they are best depicted as N-lithioaminophosphanes and not as the isomeric P-lithioiminophosphoranes.

  丁基锂 (nBuLi) 在乙醚中使 Ph2P–NHtBu 去质子化，得到 (Ph2P–NLitBu)2·OEt2。在这个分子中没有 Li…P 相互作用。三种 R'P(NLiR)2 类型的化合物已通过 R'P(NHR)2 锂化获得，分离为 [BuP(NLiPh)2·OEt2]2、[PhP(NLiPh)2·OEt2]2 和[PhP(NLiPh)2]2。nBuLi 与 MeP(NHiPr)2 在己烷/THF 中的反应导致 [MePN(Li)iPr]2·THF}4 具有不对称簇结构，包括一个 LiP3、三个 LiPN2、三个 LiP2N 和一个 LiN3 簇单元。通过 X 射线结构分析确定的这些化合物的分子结构表明，它们最好被描述为 N-锂硫氨基膦，而不是异构的 P-硫代亚氨基膦。
• Allylic Aminations with Hindered Secondary Amine Nucleophiles Catalyzed by Heterobimetallic Pd–Ti Complexes
  作者：Whitney K. Walker、Diana L. Anderson、Ryjul W. Stokes、Stacey J. Smith、David J. Michaelis

  DOI：10.1021/acs.orglett.5b00058

  日期：2015.2.6

  palladium–titanium complexes are highly effective catalysts for allylic aminations of allylic chlorides with hindered secondary amine nucleophiles. Three titanium-containing ligands are shown to assemble active catalysts in situ and enable catalysis at room temperature. A variety of sterically bulky secondary amines are efficiently allylated in high yields with as little as 1 mol % palladium catalyst. Piperidine and

  膦酰胺骨架的异双金属钯-钛络合物是高效的催化剂，用于烯丙基氯化物与受阻仲胺亲核试剂的烯丙基胺化反应。示出了三种含钛的配体在原位组装活性催化剂并能够在室温下催化。使用低至1 mol％的钯催化剂，可以高收率高效地烯丙基化各种空间庞大的仲胺。哌啶和吡咯烷产物也可通过受阻胺亲核试剂的分子内胺化而有效产生。
• Origin of Fast Catalysis in Allylic Amination Reactions Catalyzed by Pd–Ti Heterobimetallic Complexes
  作者：Whitney K. Walker、Benjamin M. Kay、Scott A. Michaelis、Diana L. Anderson、Stacey J. Smith、Daniel H. Ess、David J. Michaelis

  DOI：10.1021/jacs.5b02428

  日期：2015.6.17

  especially in the transition state. The turnover frequency of classic Pd π allyl complexes was compared to that of 1 to determine the impact of P-Pd-P coordination angle and ligand electronic properties on catalysis. These experiments identified that cationic (PPh3)2Pd(η(3)-CH2C(CH3)CH2) catalyst 3 performs similarly to 1 for allylic aminations with diethylamine. However, computations and experiment reveal

  实验和密度泛函计算用于量化用于烯丙基胺化的阳离子异双金属 Cl2Ti(N(t)BuPPh2)2Pd(η(3)-methallyl) 催化剂 1 中 Pd-Ti 相互作用的影响。Pd-Ti 相互作用的催化意义通过检查催化剂 1 的催化循环进行计算评估，该催化剂具有 Pd-Ti 相互作用完整的构象与 Pd-Ti 相互作用被切断的构象。还对阳离子单金属 (CH2)2(N(t)BuPPh2)2Pd(η(3)-甲基烯丙基) 催化剂 2 的相对反应性进行了研究，其中来自催化剂 1 的 Ti 被亚乙基取代。这些计算和实验研究表明，Pd-Ti 相互作用降低了限制营业额的胺还原添加的激活障碍，并将催化加速到 10(5)。1 中的 Pd-Ti 距离是 N(t)Bu 基团强制使两种金属靠近的船构象的结果，尤其是在过渡态。将经典 Pd π 烯丙基配合物的转换频率与 1 的转换频率进行比较，以确定 P-Pd-P 配
• Efficient Synthesis of Novel N-Substituted Bulky Diphosphinoamines
  作者：Munaka Maumela、Kevin Blann、Henriëtte de Bod、John Dixon、William Gabrielli、D. Bradley Williams

  DOI：10.1055/s-2007-990868

  日期：2007.12

  A convenient procedure for the facile preparation of electron-rich bulky diphosphinoamines from alkylamines and chlorodiphenylphosphine has been developed. The choice of solvent proved to be critical to the successful synthesis of the diphosphinoamine (PNP) products.

  开发了一种便捷的流程，用于从烷基胺和氯二苯基膦制备富含电子的大体积二膦胺。溶剂的选择被证明对成功合成二膦胺（PNP）产物至关重要。
• Nickel complexes supported by quinoline-based ligands: synthesis, characterization and catalysis in the cross-coupling of arylzinc reagents and aryl chlorides or aryltrimethylammonium salts
  作者：Qiang Zhang、Xue-Qi Zhang、Zhong-Xia Wang

  DOI：10.1039/c2dt30886j

  日期：——

  Lithium and nickel complexes bearing quinoline-based ligands have been synthesized and characterized. Reaction of 8-azidoquinoline with Ph2PNHR (R = p-MeC6H4, But) affords N-(8-quinolyl)iminophosphoranes RNHP(Ph2)N(8-C9H6N) (1a, R = p-MeC6H4; 1b, R = But. C9H6N = quinolyl)). Reaction of 1a with (DME)NiCl2 generates a nickel complex [NiCl2N(8-C9H6N)P(Ph2)NH(p-MeC6H4)}] (2a). Treatment of 1b with (DME)NiCl2 and following with NaH produces [NiCl(1,2-C6H4)P(Ph)(NHBut)N(8-C9H6N)}] (4). Complex 4 was also obtained by reaction of (DME)NiCl2 with [Li(1,2-C6H4)P(Ph)(NHBut)N(8-C9H6N)}] (5) prepared through lithiation of 1b. Reaction of 2-PyCH2P(Ph2)N(8-C9H6N) (6, Py = pyridyl) and PhNC(Ph)CH2P(Ph2)N(8-C9H6N) (8), respectively, with (DME)NiCl2 yields two five-coordinate N,N,N-chelate nickel complexes, [NiCl22-PyCH2P(Ph2)N(8-C9H6N)}] (7) and [NiCl2PhNC(Ph)CH2P(Ph2)N(8-C9H6N)}] (9). Similar reaction between Ph2PCH2P(Ph2)N(8-C9H6N) (10) and (DME)NiCl2 results in five-coordinate N,N,P-chelate nickel complex [NiCl2Ph2PCH2P(Ph2)N(8-C9H6N)}] (11). Treatment of [(8-C9H6N)NP(Ph2)]2CH2 (12) [prepared from (Ph2P)2CH2 and 2 equiv. of 8-azidoquinoline] with LiBun and (DME)NiCl2 successively affords [NiCl(8-C9H6N)NP(Ph2)}2CH] (13). The new compounds were characterized by 1H, 13C and 31P NMR spectroscopy (for the diamagnetic compounds), IR spectroscopy (for the nickel complexes) and elemental analysis. Complexes 2a, 4, 7, 9, 11 and 13 were also characterized by single-crystal X-ray diffraction techniques. The nickel complexes were evaluated for the catalysis in the cross-coupling reactions of arylzinc reagents with aryl chlorides and aryltrimethylammonium salts. Complex 7 exhibits the highest activity among the complexes in catalyzing the reactions of arylzinc reagents with either aryl chlorides or aryltrimethylammonium bromides.

  含喹啉基配体的锂和镍配合物已被合成和表征。8-叠氮喹啉与Ph2PNHR(R = p-MeC6H4, But)反应得到N-(8-喹啉基)亚氨基膦烷RNHP(Ph2)N(8-C9H6N)(1a, R = p-MeC6H4; 1b, R = But. C9H6N = 喹啉基))。1a与(DME)NiCl2反应生成镍配合物[NiCl2N(8-C9H6N)P(Ph2)NH(p-MeC6H4)}] (2a)。1b与(DME)NiCl2反应后，再用NaH处理得到[NiCl(1,2-C6H4)P(Ph)(NHBut)N(8-C9H6N)}] (4)。配合物4也可通过(DME)NiCl2与[Li(1,2-C6H4)P(Ph)(NHBut)N(8-C9H6N)}] (5)反应得到，后者是通过1b的锂化制备的。2-吡啶基甲基P(Ph2)N(8-C9H6N)(6, Py = 吡啶基)和PhNC(Ph)CH2P(Ph2)N(8-C9H6N)(8)分别与(DME)NiCl2反应，得到两个五配位的N,N,N-螯合镍配合物[NiCl22-PyCH2P(Ph2)N(8-C9H6N)}] (7)和[NiCl2PhNC(Ph)CH2P(Ph2)N(8-C9H6N)}] (9)。Ph2PCH2P(Ph2)N(8-C9H6N)(10)与(DME)NiCl2的类似反应生成五配位的N,N,P-螯合镍配合物[NiCl2Ph2PCH2P(Ph2)N(8-C9H6N)}] (11)。[(8-C9H6N)NP(Ph2)]2CH2(12)[由(Ph2P)2CH2和2当量的8-叠氮喹啉制备]依次与LiBun和(DME)NiCl2反应得到[NiCl(8-C9H6N)NP(Ph2)}2CH] (13)。新化合物通过1H、13C和31P NMR光谱(对于抗磁性化合物)、IR光谱(对于镍配合物)和元素分析进行表征。配合物2a、4、7、9、11和13还通过单晶X射线衍射技术进行表征。这些镍配合物被评估用于芳基锌试剂与芳基氯和芳基三甲基铵盐的交叉偶联反应的催化活性。在催化芳基锌试剂与芳基氯或芳基三甲基溴化铵的反应中，配合物7显示出最高的活性。