N,N'-[(3,3'-bis-tert-butyl-5,5'-bis-methoxy-1,1'-biphenyl-2,2'-diyl)phosphite]-(R,R)-1,2-diaminocyclohexane | 609365-97-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: N,N'-[(3,3'-bis-tert-butyl-5,5'-bis-methoxy-1,1'-biphenyl-2,2'-diyl)phosphite]-(R,R)-1,2-diaminocyclohexane
• 英文别名: N,N'-[bis-(3,3'-bis-tert-butyl-5,5'-bis-methoxy-1,1'-biphenyl-2,2'-diyl)phosphite]-(1R,2R)-1,2-diaminocyclohexane；R,R-1,2-bis(NHP((H3CO)(C6H2)(t-Bu)O)2)cyclohexane；(1R,2R)-1-N,2-N-bis(4,8-ditert-butyl-2,10-dimethoxybenzo[d][1,3,2]benzodioxaphosphepin-6-yl)cyclohexane-1,2-diamine
• CAS: 609365-97-1
• 化学式: C₅₀H₆₈N₂O₈P₂
• 分子量: 887.046
• InChiKey: CVRJCRFSQHAPDR-NCRNUEESSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.9
• 重原子数：
  62
• 可旋转键数：
  12
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  114
• 氢给体数：
  2
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 N,N'-[(3,3'-bis-tert-butyl-5,5'-bis-methoxy-1,1'-biphenyl-2,2'-diyl)phosphite]-(R,R)-1,2-diaminocyclohexane 以 二氯甲烷 为溶剂， 反应 0.25h， 以94%的产率得到
  参考文献：
  名称：

  用于不对称氢化的新型手性二亚磷酰胺铑（I）配合物

  摘要：

  带有（R，R）-1,2-二氨基环己烷为骨架和两个对位异构体联芳基单元的C 2对称螯合二亚磷酰胺配体的手性1,5-环辛二烯铑（I）阳离子配合物，易于合成，并通过多核单核键被充分表征以及二维NMR光谱和元素分析。这些络合物在衣康酸二甲酯，2-乙酰氨基丙烯酸甲酯和（Z）-甲基-2-乙酰氨基-3-苯基丙烯酸的不对称氢化反应中用作催化剂。衍生自含两个（R）或（S）BINOL（2,2'-dihydroxy-1,1'-binaphthyl）单元被证明是有效的催化剂，具有完全的转化率和非常好的对映选择性（高达88％ee）。在Rh络合物与含两个（S）-联萘酚部分的二磷酰胺基配体催化的衣康酸二甲酯加氢中，观察到对映选择性具有不常见的正H 2压力效应。版权所有©2014 John Wiley＆Sons，Ltd.

  DOI：

  10.1002/aoc.3170
• 作为产物：
  描述：

  4,8-di-tert-butyl-6-chloro-2,10-dimethoxy-5,7,6-dioxaphosphadibenzo[a,c]cycloheptene 、 (1R,2R)-1,2-diaminocyclohexane 在 三乙胺 作用下， 以 甲苯 为溶剂， 以80%的产率得到N,N'-[(3,3'-bis-tert-butyl-5,5'-bis-methoxy-1,1'-biphenyl-2,2'-diyl)phosphite]-(R,R)-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

• Chiral cyclopentadienyl ruthenium(II) complexes with P,P-ligands derived from (1R,2R)-1,2-diaminocyclohexane: Synthesis, crystal structures and catalytic activity in Diels–Alder reactions
  作者：Carmela G. Arena、Giuseppe Bruno、Francesco Nicolò

  DOI：10.1016/j.poly.2010.07.002

  日期：2010.9

  Chiral cyclopentadienyl ruthenium(II) complexes [CpRu(L1-L3)Cl] (5-7) have been prepared by reaction of (CpRu(PPh3)(2)Cl] with chiral P,P-ligands (1R,2R)-1,2-bis(diphenylphosphinamino)cyclohexane (L1), N,N'-[bis-(3,3'-bis-tert-butyl-5,5'-bis-methoxy-1,1'-biphenyl-2,2'-diyl)phosphite]-(1R,2R)-1,2-diaminocyclohexane (L2) and N,N'-[bis-(R)-1,1'-binaphtyl-2,2'-diyl)phosphite]-(1R,2R)-1,2-diaminocyclohexane (L3). The molecular structures of 5 and 6 have been determined by single-crystal X-ray analysis. Studies on catalytic activity of the cations derived from (5-7) by treatment with AgSbF6, are also reported. (C) 2010 Elsevier Ltd. 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.
• 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 diphosphoramidite rhodium(I) complexes for asymmetric hydrogenation
  作者：Dario Drommi、Giuseppe Micalizzi、Carmela Grazia Arena

  DOI：10.1002/aoc.3170

  日期：2014.8

  Chiral 1,5‐cyclooctadiene rhodium(I) cationic complexes with C2‐symmetric chelate diphosphoramidite ligands containing (R,R)‐1,2‐diaminocyclohexane as the backbone and two atropoisomeric biaryl units were easily synthesized and fully characterized by multinuclear one‐ and two‐dimensional NMR spectroscopy and elemental analysis. These complexes were used as catalysts in the asymmetric hydrogenation

  带有（R，R）-1,2-二氨基环己烷为骨架和两个对位异构体联芳基单元的C 2对称螯合二亚磷酰胺配体的手性1,5-环辛二烯铑（I）阳离子配合物，易于合成，并通过多核单核键被充分表征以及二维NMR光谱和元素分析。这些络合物在衣康酸二甲酯，2-乙酰氨基丙烯酸甲酯和（Z）-甲基-2-乙酰氨基-3-苯基丙烯酸的不对称氢化反应中用作催化剂。衍生自含两个（R）或（S）BINOL（2,2'-dihydroxy-1,1'-binaphthyl）单元被证明是有效的催化剂，具有完全的转化率和非常好的对映选择性（高达88％ee）。在Rh络合物与含两个（S）-联萘酚部分的二磷酰胺基配体催化的衣康酸二甲酯加氢中，观察到对映选择性具有不常见的正H 2压力效应。版权所有©2014 John Wiley＆Sons，Ltd.