(S,S)-N,N'-bis[o-(diphenylphosphino)benzylidene]-1,2-diaminocyclohexane

• 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: (S,S)-N,N'-bis[o-(diphenylphosphino)benzylidene]-1,2-diaminocyclohexane
• 英文别名: (S,S)-N,N'-bis[o-(diphenylphosphino)benzylidene]cyclohexane-1,2-diamine；N,N'-bis[o-(diphenylphosphino)benzylidene]-(1S,2S)-diiminocyclohexane；N,N'-bis[o-(diphenylphosphino)benzylidene]-1S,2S-diiminocyclohexane；(1S)-1alpha,2beta-Bis[2-(diphenylphosphino)benzylideneamino]cyclohexane；1-(2-diphenylphosphanylphenyl)-N-[(1S,2S)-2-[(2-diphenylphosphanylphenyl)methylideneamino]cyclohexyl]methanimine
• 化学式: C₄₄H₄₀N₂P₂
• 分子量: 658.763
• InChiKey: GCUKRENTSKVSIL-COCZKOEFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.4
• 重原子数：
  48
• 可旋转键数：
  10
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  tris(triphenylphosphine)ruthenium(II) chloride 、 (S,S)-N,N'-bis[o-(diphenylphosphino)benzylidene]-1,2-diaminocyclohexane 以 二氯甲烷 为溶剂， 以91%的产率得到RuCl2(κ4-N,N'-bis[o-(diphenylphosphino)benzylidene]-(1S,2S)-diiminocyclohexane)
  参考文献：
  名称：

  手性四齿P 2 N 2配体的钌（II）配合物催化烯烃与H 2 O 2的不对称环氧化

  摘要：

  通过从[RuCl 2（PNNP）]中提取氯来制备[RuCl（PNNP）] PF 6类型的五配位络合物（PNNP =具有P 2 N 2供体的四齿配体）。Δ-的混合物的顺式-β-和Λ-顺-β-将[RuCl 2（1A -κ 4 P，N，N，P）]（2A ; 1A = N， “双[ ø - （二苯基膦基）亚苄基] -2,2'-二亚氨基-1,1'-（S）-联萘），是通过1a与[RuCl 2（PPh 3）3]，其中铊[PF发生反应6 ]，给五配位化合物[RuCl（1A -κ 4 P，N，N，P）] PF 6（图3a）。相关的反式-将[RuCl 2（1B -κ 4 P，N，N，P）]（2b中;图1b = N， “双[ ø - （二苯基膦基）亚苄基] - （1-小号，2小号）-diiminocyclohexane ）用铊[PF进行反应6 ]，得到将[RuCl（1B -κ 4 P，N，N，P）] PF 6（图3b）。与氨基配体N，N-

  DOI：

  10.1021/om000481v
• 作为试剂：
  描述：

  N-(1-furylethylidene)diphenylphosphinamide 在 (S,S)-N,N'-bis[o-(diphenylphosphino)benzylidene]-1,2-diaminocyclohexane 、 [NEt₃H][HFe₃(CO)₁₁] 、 potassium hydroxide 作用下， 以 异丙醇 为溶剂， 反应 1.0h， 以67%的产率得到N-[(1R)-1-furylethyl]-P,P-diphenylphosphinic amide
  参考文献：
  名称：

  胺的对映选择性合成：亚胺的一般高效铁催化不对称转移加氢

  摘要：

  在铁器时代：一种易于获得的活性铁催化剂可用于亚胺的直接催化转移加氢（参见方案）。一系列亚胺以高收率和非常好的对映选择性被转化为手性胺。该方法应在寻找生物活性手性胺中找到广泛的应用。

  DOI：

  10.1002/anie.201002456

文献信息

• Highly efficient chiral metal cluster systems derived from Ru3(CO)12 and chiral diiminodiphosphines for the asymmetric transfer hydrogenation of ketones
  作者：Hui Zhang、Chuan-Bo Yang、Yan-Yun Li、Zhen-Rong Donga、Jing-Xing Gao、Hideaki Nakamura、Kunihiko Murata、Takao Ikariya

  DOI：10.1039/b209974h

  日期：2003.12.19

  The chiral Ru cluster-based catalyst systems generated in situ from Ru3(CO)12 and chiral diiminodiphosphine tetradentate ligands effected asymmetric transfer hydrogenation of propiophenone in 2-propanol, leading to 1-phenyl-1-propanol in 94% yield and with 96% ee.

  由Ru3（CO）12和手性二亚氨基二膦四齿配体原位生成的基于手性Ru团簇的催化剂体系实现了苯丙酮在2-丙醇中的不对称转移加氢，从而产生1-苯基-1-丙醇，产率为94％，产率为96％ ee。
• Preparation of chiral diimino- and diaminodiphosphine ligands and their CuI and AgI complexes. X-ray crystal structures of [Cu(1S,2S-cyclohexyl-P2N2)][PF6] and [Ag(1R,2R-cyclohexyl-P2N2H4)][BF4]
  作者：Wai-Kwok Wong、Tat-Wai Chik、Kin-Ning Hui、Ian Williams、Xue Feng、Thomas C.W. Mak、Chi-Ming Che

  DOI：10.1016/0277-5387(96)00196-9

  日期：1996.9

  tetradentate ligand undergoes rapid dissociation to form a tridentate ligand. The interaction of AgBF4 with 1 equiv. of otpically pure L 4 [ L 4 = (R,R)- I , (S,S)- I , (R,R)- II and (S,S)- II gave the corresponding optically pure [AgL4][BF4] complexes, VII–X VII L 4 = (R,R)- I ; VIII , L 4 = (S,S)- I ; IX ,L 4 = (R,R)- II ; X, L 4 = (S,S)- II ] , in good yield. For the AgI complexes, the L4 ligand acted

  摘要光学纯的1R，2R-二铵环己烷单-（酒石酸）酒石酸盐与1S，2S-二铵环己烷单-（-）-酒石酸盐的当量相互作用。在2当量存在下的邻-（二苯基膦基）苯甲醛 回流的乙醇/水混合物中加碳酸钾得到光学纯的缩合产物N，N′-双[邻-（（二苯基膦基）亚苄基] -1R，2R-二亚氨基环己烷[1R，2R-环己基-P 2 N 2，（R ，R）-I]和N，N′-双[邻-（（二苯基膦基）亚苄基] -1S，2S-二亚氨基环己烷[1S，2S-环己基-P 2 N 2，（S，S）-I]，产量高。在乙醇中用NaBH4还原光学纯的（R，R）-I和（S，S）-I，得到光学纯的还原产物N，N'-双[o-（（二苯基膦基）亚苄基] -1R，2R-二氨基环己烷[ 1R，2R-环己基-P2N2H4，（R，R）-II]和N，N′-双[邻-二苯基膦）亚苄基] -1S，分别以良好的收率得到2S-二氨基环己烷[1S，2S-环己基-P 2 N
• New chiral cationic rhodium–aminophosphine complexes for asymmetric transfer hydrogenation of aromatic ketones
  作者：Jing-Xing Gao、Xiao-Dong Yi、Pian-Pian Xu、Chun-Liang Tang、Hui-Lin Wan、Takao Ikariya

  DOI：10.1016/s0022-328x(99)00565-3

  日期：1999.12

  The new chiral ligands (S,S)-N,N'-bis[o-(diphenylphosphino)benzylidene]1,2-diiminocyclohexane, [(S,S)-1] and (S,S)-N,N'-bis[o-diphenylphosphino]benzyl-1,2-diaminocyclohexane, [(S,S)-2] have been prepared. The interaction of [(S,S)-1] and [(S,S)-2] with [Rh(COD)Cl](2) afforded the corresponding cationic rhodium complexes [(S,S)-3][X] and [(S,S)-4][X] (X = PF6-, BF4- or ClO4-), respectively. [(S,S)-1], [(S,S)-2], [(S,S)-3][X] and [(S,S)-4][X] have been fully characterized by elemental analyses and spectroscopic methods. These chiral cationic rhodium complexes serve as catalytst precursors for the asymmetric transfer hydrogenation of acetophenone derivatives in 2-propanol and [(S,S)-4][PF6] acts as an excellent catalyst in the reduction of m-chloroacetophenone, giving the corresponding optical alcohols in 99% yield and up to 94% ee. (C) 1999 Elsevier Science S.A. All rights reserved.
• A Ruthenium(II) Complex with a <i>C</i>₂-Symmetric Diphosphine/Diamine Tetradentate Ligand for Asymmetric Transfer Hydrogenation of Aromatic Ketones
  作者：Jing-Xing Gao、Takao Ikariya、Ryoji Noyori

  DOI：10.1021/om950833b

  日期：1996.2.20

  The trans-(RuCl2)-Cl-II complexes with structurally similar N,N'-bis[o-(diphenylphosphino)benzylidene]cyclohexane-1,2-diamine and N,N'-bis[o-(diphenylphosphino)-benzyl]cyclohexane-1,2-diamine ligands have been synthesized, and their molecular structures have been determined. The C-2-symmetric diphosphine/diamine-based Ru complex acts as an excellent catalyst precursor in asymmetric transfer hydrogenation of acetophenone in a 0.1 M 2-propanol solution, leading to 2-phenylethanol in 97% ee and in 93% yield after 7 h at 45 degrees C. This transfer hydrogenation is characterized by low reversibility under these conditions.
• Ruthenium(II) Complexes with Chiral Tetradentate P₂N₂ Ligands Catalyze the Asymmetric Epoxidation of Olefins with H₂O₂
  作者：Robert M. Stoop、Stephan Bachmann、Massimiliano Valentini、Antonio Mezzetti

  DOI：10.1021/om000481v

  日期：2000.10.1

  2S)-diaminocyclohexane (1c), the aqua complex [RuCl(OH2)(1c-κ4P,N,N,P)]PF6 (5c) is obtained by reaction of Tl[PF6] with [RuCl2(PPh3)(1c-κ3P,N,N)] (4), which has been isolated and structurally characterized. The reactivity of the five-coordinate 2b with CO and oxygen donors such as water, Et2O, THF, and methanol is reported. Both 3 and 5 catalyze the asymmetric epoxidation of olefins with hydrogen peroxide as oxidant

  通过从[RuCl 2（PNNP）]中提取氯来制备[RuCl（PNNP）] PF 6类型的五配位络合物（PNNP =具有P 2 N 2供体的四齿配体）。Δ-的混合物的顺式-β-和Λ-顺-β-将[RuCl 2（1A -κ 4 P，N，N，P）]（2A ; 1A = N， “双[ ø - （二苯基膦基）亚苄基] -2,2'-二亚氨基-1,1'-（S）-联萘），是通过1a与[RuCl 2（PPh 3）3]，其中铊[PF发生反应6 ]，给五配位化合物[RuCl（1A -κ 4 P，N，N，P）] PF 6（图3a）。相关的反式-将[RuCl 2（1B -κ 4 P，N，N，P）]（2b中;图1b = N， “双[ ø - （二苯基膦基）亚苄基] - （1-小号，2小号）-diiminocyclohexane ）用铊[PF进行反应6 ]，得到将[RuCl（1B -κ 4 P，N，N，P）] PF 6（图3b）。与氨基配体N，N-