N-cyclohexyl-1,1-diphenylphosphinecarboxamide | 1410202-97-9

• 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-cyclohexyl-1,1-diphenylphosphinecarboxamide
• 英文别名: N-cyclohexyl-1-diphenylphosphanylformamide
• CAS: 1410202-97-9
• 化学式: C₁₉H₂₂NOP
• 分子量: 311.364
• InChiKey: NZZVTZUHYBUKLH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  N-cyclohexyl-1,1-diphenyl-N-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phosphinecarboxamide 以 甲醇 为溶剂， 反应 0.5h， 以86%的产率得到N-cyclohexyl-1,1-diphenylphosphinecarboxamide
  参考文献：
  名称：

  碳二亚胺，异氰酸酯，异硫氰酸酯和CO 2的膦酰基硼化

  摘要：

  已经研究了膦基硼酸酯Ph 2 PBpin（pin = 1,2-O 2 C 2 Me 4）向包括碳二亚胺，异氰酸酯，异硫氰酸酯和二氧化碳的杂聚枯烯的无过渡金属加成。相应的1，2-加成产物易于在室温下制备，不需要催化剂或添加的碱。在将Ph 2 PBpin加到碳二亚胺，异氰酸酯和异硫氰酸酯中而得的化合物中添加甲醇，得到了传统的加氢磷酸化产物。这项研究中开发的方法为生成各种功能化的膦提供了一条简单而优雅的途径。膦基硼酸酯Ph 2PBpin还在室温下以1,2-方式选择性地和可逆地添加到CO 2中。

  DOI：

  10.1039/c7dt02305g

文献信息

• Insertion Reactions and Catalytic Hydrophosphination of Heterocumulenes using α-Metalated <i>N</i>,<i>N</i>-Dimethylbenzylamine Rare-Earth-Metal Complexes
  作者：Andrew C. Behrle、Joseph A. R. Schmidt

  DOI：10.1021/om300807k

  日期：2013.3.11

  dimethylbenzylamine) was probed through a series of stoichiometric insertion and catalytic hydrophosphination reactions. Both rare-earth-metal species inserted 3 equiv of various carbodiimides to form the corresponding homoleptic amidinates. α-La(DMBA)3 was also found to be a useful precatalyst for the room-temperature hydrophosphination of heterocumulenes to form phosphaguanidines, phosphaureas, and phosphathioureas

  通过一系列化学计量插入和催化加氢磷酸化反应，探查了均相的α-金属化的二甲基苄基胺镧系元素络合物（α - Ln（DMBA）3； Ln = La，Y; DMBA =α-去质子化的二甲基苄胺）的反应性。两种稀土金属物种都插入了3个当量的各种碳二亚胺，以形成相应的均化eptic胺盐。α - La（DMBA）3还发现其以适中至优异的分离产率，对于杂枯烯的室温氢磷酸化以形成磷胍，磷酰脲和硫代硫脲是有用的预催化剂。此外，通过一系列逐步的化学计量质子化和插入反应，研究了氢磷化催化的合理机理。
• Iron(II)-Catalyzed Hydrophosphination of Isocyanates
  作者：Helen R. Sharpe、Ana M. Geer、William Lewis、Alexander J. Blake、Deborah L. Kays

  DOI：10.1002/anie.201701051

  日期：2017.4.18

  The first transition metal catalyzed hydrophosphination of isocyanates is presented. The use of low‐coordinate iron(II) precatalysts leads to an unprecedented catalytic double insertion of isocyanates into the P−H bond of diphenylphosphine to yield phosphinodicarboxamides [Ph2PC(=O)N(R)C(=O)N(H)R], a new family of derivatized organophosphorus compounds. This remarkable result can be attributed to the

  提出了第一过渡金属催化的异氰酸酯加氢磷酸化。低配位铁（II）预催化剂的使用导致异氰酸酯前所未有地催化双插入双苯基膦的PH键中，从而生成膦二羧酸酰胺[Ph 2 PC（= O）N（R）C（= O）N（ H）R]，一种新的衍生化有机磷化合物家族。这一非凡的结果可归因于铁（II）中心的低配位性质，其固有的电子缺陷使路易斯酸机制得以发挥作用，在该机制中，金属中心的空间穴和底物尺寸的组合决定了反应产物和区域选择性。
• An efficient catalytic method for hydrophosphination of heterocumulenes with diethylzinc as precatalyst without a solvent
  作者：Bingyi Zhang、Xiaoli Ma、Ben Yan、Congjian Ni、Hailong Yu、Zhi Yang、Herbert W. Roesky

  DOI：10.1039/d1dt02706a

  日期：——

  Commercially available compound ZnEt2 acts as an efficient precatalyst for the solvent-free hydrophosphinations of heterocumulenes using Ph2PH as reagent. As far as we knew, this has been not reported in group 12 metal catalyzing reactions. A suggested mechanism of this reaction is explored, and the intermediate [Ph2PC(NiPr)2}ZnEt]2 is obtained and characterized by a single-crystal X-ray structural

  市售化合物 ZnEt 2作为一种有效的预催化剂，用于使用 Ph 2 PH 作为试剂的杂枯草烯的无溶剂氢膦化反应。据我们所知，这在第 12 族金属催化反应中尚未见报道。探索了该反应的建议机制，获得了中间体 [Ph 2 PC(N i Pr) 2 }ZnEt] 2并通过单晶 X 射线结构分析对其进行了表征。
• The first ring-expanded NHC–copper(<scp>i</scp>) phosphides as catalysts in the highly selective hydrophosphination of isocyanates
  作者：Thomas M. Horsley Downie、Jonathan W. Hall、Thomas P. Collier Finn、David J. Liptrot、John P. Lowe、Mary F. Mahon、Claire L. McMullin、Michael K. Whittlesey

  DOI：10.1039/d0cc05694d

  日期：——

  first reports of ring-expanded NHC–copper(I) phosphides. The compounds were characterised by NMR spectroscopy and X-ray crystallography. Reaction of (6-Dipp)CuPPh2 with isocyanates, isothiocyanates and carbon disulfide results in the insertion of the heterocumulene into the Cu–P bond. The NHC–copper phosphides were found to be the most selective catalysts yet reported for the hydrophosphination of isocyanates

  合成了一系列N-杂环卡宾负载的铜二苯基磷化物（NHC = IPr，6-Dipp，SIMes和6-Mes）。其中包括有关环扩NHC-铜（I）磷化物的首次报道。通过NMR光谱和X射线晶体学对化合物进行表征。（6-Dipp）CuPPh 2与异氰酸酯，异硫氰酸酯和二硫化碳的反应导致杂茂基插入Cu-P键中。人们发现，NHC-磷化铜是对异氰酸酯进行加氢磷酸化的最具选择性的催化剂。它们以优异的转化率和良好的收率提供了广泛的膦酰基羧酰胺。
• Synthesis of Bis(NHC)-Based CNC-Pincer Rare-Earth-Metal Amido Complexes and Their Application for the Hydrophosphination of Heterocumulenes
  作者：Xiaoxia Gu、Lijun Zhang、Xiancui Zhu、Shaowu Wang、Shuangliu Zhou、Yun Wei、Guangchao Zhang、Xiaolong Mu、Zeming Huang、Dongjing Hong、Feng Zhang

  DOI：10.1021/acs.organomet.5b00628

  日期：2015.9.28

  The bis(NHC) (NHC = N-heterocyclic carbene)-based CNC-pincer rare-earth-metal amido complexes LRE[N(SiMe3)(2)](2) (L = 4-CH3-2-R-[N(CH)(2)CN]}C6H3](2)N; L2, R = CH3; L3, R = CH(CH3)(2)) were synthesized and characterized, and their catalytic activities toward hydrophosphination of heterocumulenes were developed. Reactions of bis[2-(3-methylimidazolium)-4-methylphenyl]amine diiodide (H3L2I(2)) or bis[2-(3-isopropylimidazolium)-4-methylphenyl]amine diiodide (H3L2I(2)) with 5 equiv of NaN(SiMe3)(2) followed by treatment with 1 equiv of RECl3 in THF at -78 C afforded the bis(NHC)-based CNC-pincer rare-earth-metal amido complexes LRE[N(SiMe3)(2)](2) (L2 = [4-CH3-2-CH3-[N(CH)(2)CN]}C6H3](2)N, RE = Y (1), Eu (2), Er (3); L-3 = [4-CH3-2-(CH3)(2)CH-[N(CH)(2)CN]}C6H3](2)N, RE = Y (4), Er (5), Yb (6)). Complexes 46 can also be prepared by stepwise reactions of H3L-3I-2 with n-BuLi in THF followed by reactions with [(Me3Si)2N]3RE(mu-Cl)Li(THF)3. Stepwise reactions of H3L3I(2) with n-BuLi in THF followed by treatment with [(Me3Si)(2)N](3)RE(mu-Cl)Li(THF)(3) generated the bis(NHC)-based CNC-pincer rare-earth-metal amido complexes L2RE[N-(SiMe3)(2)](2) (RE = Y (1), Er (3)) together with the fused-heterocyclic compound 3,8,9-trimethyl-8a,9-dihydro-8H-benzo[4,5]imidazo[2',1':2,3]imidazo[1,2-a]imidazo[2,1-c]quinoxaline (7), which formed through carbene CC and CN coupling. Attempts to prepare complexes of the type LRE[N(SiMe3)(2)](2) by reaction of H3L3I(2) with [(Me3Si)(2)N](3)Yb(mu-Cl)Li(THF)(3) in THF, however, afforded mixed complexes of the bis(NHC)-based CNC-pincer ytterbium complex L3Yb[N(SiMe3)(2)](2) (6) and the unexpected bis(NHC)-based CNC-pincer monoamido ytterbium iodide L3YbI[N(SiMe3)(2)] (8). Investigation of the catalytic activity of complexes 16 and 8 indicated that all complexes displayed high activity toward the addition of the phosphine PH bond to heterocumulenes, producing the corresponding phosphaguanidines, phosphaureas, and phosphathioureas, which represents the first example of bis(NHC)-based CNC-pincer type rare-earth-metal amido complexes as catalysts for the catalytic addition of the phosphine PH bond to heterocumulenes with high efficiency in the presence of a low catalyst loading at room temperature