N-[(3,3'-bis-tert-butyl-5,5'-bis-methoxy-1,1'-biphenyl-2,2'-diyl)phosphate]-(R,R)-N,N'-dimethyl-1,2-diaminocyclohexane | 609365-95-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: N-[(3,3'-bis-tert-butyl-5,5'-bis-methoxy-1,1'-biphenyl-2,2'-diyl)phosphate]-(R,R)-N,N'-dimethyl-1,2-diaminocyclohexane
• 英文别名: R,R-1-(NHCH3)-2-(N(CH3)P((H3CO)(C6H2)(t-Bu)O)2)cyclohexane；(1R,2R)-2-N-(4,8-ditert-butyl-2,10-dimethoxybenzo[d][1,3,2]benzodioxaphosphepin-6-yl)-1-N,2-N-dimethylcyclohexane-1,2-diamine
• CAS: 609365-95-9
• 化学式: C₃₀H₄₅N₂O₄P
• 分子量: 528.672
• InChiKey: QDVRWHPMJHHFIR-CLJLJLNGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.8
• 重原子数：
  37
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  60
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  N-[(3,3'-bis-tert-butyl-5,5'-bis-methoxy-1,1'-biphenyl-2,2'-diyl)phosphate]-(R,R)-N,N'-dimethyl-1,2-diaminocyclohexane 、 chloro(1,5-cyclooctadiene)rhodium(I) dimer 以 not given 为溶剂， 生成 [Rh(cycloocta-1,5-diene)(R,R-1-(NHCH3)-2-(N(CH3)P((H3CO)(C6H2)(t-Bu)O)2)cyclohexane)]Cl
  参考文献：
  名称：

  Chiral rhodium complexes containing bidentate ligands derived from (R,R)-1,2-diaminocyclohexane for catalytic enantioselective hydrosilylation of acetophenone

  摘要：

  Bidentate P,P- and N,P-ligands derived from inexpensive and commercially available chiral source (R,R)-1,2-diaminocyclohexane, have been tested in the asymmetric Rh-catalyzed addition of diphenylsilane to acetophenone. Studies on the reactivity of these ligands towards the rhodium precursor [Rh(cod)Cl](2) (cod = cycloocta-1,5-diene) have shown that either monomeric, or dinuclear complexes, or both can be found in the solution. The structure of the cationic complex [Rh(cod)(3a)]PF6 (12), has been elucidated by X-ray analysis. The presence in the reaction mixture of different rhodium complexes which act as precatalysts, influences the activity and stereoselectivity of the process. (C) 2004 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2004.07.012
• 作为产物：
  描述：

  (1R,2R)-(-)-N,N'-二甲基-1,2-环己二胺 、 4,8-di-tert-butyl-6-chloro-2,10-dimethoxy-5,7,6-dioxaphosphadibenzo[a,c]cycloheptene 在 三乙胺 作用下， 以 甲苯 为溶剂， 以85%的产率得到N-[(3,3'-bis-tert-butyl-5,5'-bis-methoxy-1,1'-biphenyl-2,2'-diyl)phosphate]-(R,R)-N,N'-dimethyl-1,2-diaminocyclohexane
  参考文献：
  名称：

  New chiral amino-phosphoramidite and bisphosphoramidite ligands derived from (R,R)-1,2-diaminocyclohexane: application in Cu-catalyzed asymmetric conjugate addition of diethylzinc to 2-cyclohexenone

  摘要：

  New bidentate amino-phosphoroamidite and diphosphoroamidite ligands derived from inexpensive (R,R)-1,2-diaminocyclohexane have been synthesized and screened in the Cu-catalyzed asymmetric conjugate addition of Et2Zn to 2-cyclohexenone. The highest 74% ee value was reached with the N,N'-dimethyl substituted P,N-ligand and Cu(OAc)(2).H2O. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(03)00447-6

文献信息

• Half-sandwich ruthenium(II) and rhodium(III) complexes bearing chiral amino-phosphoramidite ligands: Synthesis, characterization and application in asymmetric transfer hydrogenation of acetophenone
  作者：Carmela Grazia Arena、Angela Cuzzola、Dario Drommi

  DOI：10.1016/j.poly.2012.08.066

  日期：2012.11

  Abstract Cationic (η6-p-cymene) ruthenium(II) and (η5-C5Me5) rhodium(III) complexes containing chiral chelate P,N ligands (1R,2R)-N1-(4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)-N1,N2-dialkylcyclohexane-1,2-diamine (alkyl = Me L1, Et L2) have been synthesized and characterized by multinuclear one- and two-dimensional NMR spectroscopy, conductivity measurements, mass spectroscopy

  摘要含有手性螯合P，N配体（1R，2R）-N1-（4,8-二叔丁基-合成并表征了2,10-二甲氧基二苯并[d，f] [1,3,2]二氧杂磷酰基-6-基）-N1，N2-二烷基环己烷-1,2-二胺（烷基= Me L1，Et L2）多核一维和二维NMR光谱，电导率测量，质谱和元素分析。在钌配合物[Ru（η6-p-cymene）（κ-P，κ-N）-（L1-L2）Cl] SbF6 1-2的情况下，形成具有S⩾构型的SRu非对映异构体98％。对于铑配合物[Rh（η5-C5Me5）（κ-P，κ-N）-（L1-L2）Cl] SbF6 3-4，螯合过程的立体选择性和配合物的构型稳定性取决于反应条件和氨基氮的N-取代基。
• Chiral rhodium complexes containing bidentate ligands derived from (R,R)-1,2-diaminocyclohexane for catalytic enantioselective hydrosilylation of acetophenone
  作者：Carmela G. Arena、Roberto Pattacini

  DOI：10.1016/j.molcata.2004.07.012

  日期：2004.11

  Bidentate P,P- and N,P-ligands derived from inexpensive and commercially available chiral source (R,R)-1,2-diaminocyclohexane, have been tested in the asymmetric Rh-catalyzed addition of diphenylsilane to acetophenone. Studies on the reactivity of these ligands towards the rhodium precursor [Rh(cod)Cl](2) (cod = cycloocta-1,5-diene) have shown that either monomeric, or dinuclear complexes, or both can be found in the solution. The structure of the cationic complex [Rh(cod)(3a)]PF6 (12), has been elucidated by X-ray analysis. The presence in the reaction mixture of different rhodium complexes which act as precatalysts, influences the activity and stereoselectivity of the process. (C) 2004 Elsevier B.V. All rights reserved.
• New chiral amino-phosphoramidite and bisphosphoramidite ligands derived from (R,R)-1,2-diaminocyclohexane: application in Cu-catalyzed asymmetric conjugate addition of diethylzinc to 2-cyclohexenone
  作者：Carmela G. Arena、Vincenzo Casilli、Felice Faraone

  DOI：10.1016/s0957-4166(03)00447-6

  日期：2003.8

  New bidentate amino-phosphoroamidite and diphosphoroamidite ligands derived from inexpensive (R,R)-1,2-diaminocyclohexane have been synthesized and screened in the Cu-catalyzed asymmetric conjugate addition of Et2Zn to 2-cyclohexenone. The highest 74% ee value was reached with the N,N'-dimethyl substituted P,N-ligand and Cu(OAc)(2).H2O. (C) 2003 Elsevier Ltd. All rights reserved.