N,N-bis(diphenylphosphine)-(S_c)-sec-butylamine | 697288-71-4

• 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,N-bis(diphenylphosphine)-(S_c)-sec-butylamine
• 英文别名: (Sc)-N,N-bis(diphenylphosphanyl)-sec-butylamine；N,N-bis(diphenylphosphino)-(Sc)-sec-butylamine；(2S)-N,N-bis(diphenylphosphanyl)butan-2-amine
• CAS: 697288-71-4
• 化学式: C₂₈H₂₉NP₂
• 分子量: 441.492
• InChiKey: FIOZIVFNFRTUGH-DEOSSOPVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.6
• 重原子数：
  31
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  dichloro( 1,5-cyclooctadiene)platinum(ll) 、 N,N-bis(diphenylphosphine)-(S_c)-sec-butylamine 以 二氯甲烷 为溶剂， 以82%的产率得到platinum(II) (Sc)-N,N-bis(diphenylphosphanyl)-sec-butylamine dichloride
  参考文献：
  名称：

  Rhodium( I ), Palladium( II ) and Platinum( II ) Coordination Chemistry of the Short‐Bite Chiral Ligands ( S _c )‐ N , N ‐Bis(diphenylphosphanyl)‐ sec ‐butylamine, ( R _a , R _a )‐ N , N ‐Bis(binaphthylphosphonito)phenylamine and ( R _a , S _c )‐ N ‐(Diphenylphosphanyl)‐ N ‐(binaphthylphosphonito)‐ sec ‐butylamine

  摘要：

  AbstractThe new short‐bite chiral ligands (Sc)‐N,N‐bis(diphenylphosphanyl)‐sec‐butylamine [(Sc)‐1], (Ra,Ra)‐N,N‐bis(binaphthylphosphonito)phenylamine [(Ra,Ra)‐2] and (Ra,Sc)‐N‐(diphenylphosphanyl)‐N‐(binaphthylphosphonito)‐sec‐butylamine [(Ra,Sc)‐3] have been treated with rhodium(I), palladium(II) and platinum(II) substrates. The (Sc)‐1 ligand reacts with [Pd(C6H5CN)2Cl2], [Pt(COD)Cl2] and [Rh(COD)(THF)2]PF6 to afford the products [Pd(Sc‐1)Cl2] (4), [Pt(Sc‐1)Cl2] (5) and [Rh(COD)(Sc‐1)]PF6 (6), respectively, in high yields. By bubbling CO to a CH2Cl2 solution of 6, we formed the dicarbonyl species [Rh(CO)2(Sc‐1)]PF6 (7), which is stable only in solution under CO. Compounds 4 and 5 were characterized additionally by X‐ray diffraction studies. The ligand (Ra,Ra)‐2 reacts with [Pd(C6H5CN)2Cl2] and [Pt(COD)I2] to give [Pd(Ra,Ra‐2)Cl2] (8) and [Pt(Ra,Ra‐2)I2] (9), respectively; the reaction with [Rh(CO)2Cl]2 or [Rh(COD)(THF)2]PF6 affords a mixture of mono‐ and binuclear compounds, in which the ligand is oxidized to the corresponding phosphonate or is partially hydrolysed. The compounds [Pd(Ra,Sc‐3)Cl2] (10) and [Pt(Ra,Sc‐3)I2] (11) were obtained in the analogous reactions using the asymmetric (Ra,Sc)‐3 ligand. This ligand reacted with [Rh(CO)2Cl]2 in a 2:1 molar ratio in hexane to give a mixture of products in almost equal amounts. The 31P{1H} NMR spectrum recorded in CDCl3 allowed us to identify the chelate [Rh(Ra,Sc‐3)(CO)Cl] (12); the nature of the accompanying dinuclear species 13 is not clear. The catalytic systems formed by [Rh(acac)(CO)2] and the ligands (Ra,Ra)‐2 and (Ra,Sc)‐3, at ligand/metal ratios of 1:1 and 1:2, were unstable under the experimental conditions used (CO/H2 pressure of 50 atm and temperature of 40 °C) for the hydroformylation of styrene; instead, metallic rhodium was afforded together with unidentified decomposition products. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

  DOI：

  10.1002/ejic.200300568
• 作为产物：
  描述：

  (S)-(+)-2-氨基丁烷 、 二苯基氯化膦 在 三乙胺 作用下， 以 甲苯 为溶剂， 以75%的产率得到N,N-bis(diphenylphosphine)-(S_c)-sec-butylamine
  参考文献：
  名称：

  Effect of chelating vs. bridging coordination of chiral short-bite P–X–P (X = C, N, O) ligands in enantioselective palladium-catalysed allylic substitution reactions

  摘要：

  手性短咬合配体(Ra,Ra)-双(二萘基膦)甲烷、(Ra,Ra)-1、(Ra,Ra)-双二萘基焦磷酸、(Ra,Ra)-2、(Sc)-双(二苯基膦)-仲丁胺、(Sc)-3、(Ra、(Ra,Ra)-4a、(Ra,Ra,Sc)-双(二萘基膦)-仲丁胺(Ra,Ra,Sc)-4b 和(Ra,Sc)-(二萘基膦)(二苯基膦)-仲丁胺(Ra,Sc)-5。阳离子钯烯丙基单核螯合物 [Pd(δ-3-PhCHCHPh)(δ-LâLshort-bite)]PF6[LâLshort-bite = (Sc)-3、(Ra,Ra)-4a、(Ra、(Ra,Ra)-4a、(Ra,Ra,Sc)-4b 和 (Ra,Sc)-5]以及双核桥联的[Pd(δ-3-PhCHCHPh)(δ-Ra,Ra-2)]2(PF6)2, 12。合成的短口手性配体在 1,3-二苯基烯丙基乙酸酯与丙二酸二甲酯的钯烯丙基催化取代反应中进行了测试。我们采用多核核磁共振技术对溶液中的催化体系进行了研究。在(Ra,Ra)-2 配体形成的催化活性物质 [Pd(δ-3-PhCHCHCHPh)(Ra,Ra-2)]2(PF6)2,12中，钯（II）中心被两个配体桥接，这两个配体被迫采用近似顺式配位，以便烯丙基配位。对类似于 12 物种的联苯模型分子进行的半经验计算表明，这种情况会导致手性配体的应变和刚性构象，从而产生末端烯丙基碳原子的差异。因此，S 型催化产物的对映体过量率为 57.1%。在相同的钯催化反应中，当测试 (Ra,Ra)-1、(Sc)-3、(Ra,Ra)-4a、(Ra,Ra,Sc)-4b 和 (Ra,Sc)-5 配体时，得到的对映体过量值较低。

  DOI：

  10.1039/b309385a