(R,R)-bis(diphenylthiophosphoramino)-1,2-cyclohexane

• 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: (R,R)-bis(diphenylthiophosphoramino)-1,2-cyclohexane
• 英文别名: (1R,2R)-1-N,2-N-bis(diphenylphosphinothioyl)cyclohexane-1,2-diamine
• 化学式: C₃₀H₃₂N₂P₂S₂
• 分子量: 546.677
• InChiKey: AJEQCKWWYJOAJP-LOYHVIPDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.1
• 重原子数：
  36
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  88.2
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tetrakis(dimethylamido)titanium(IV) 、 (R,R)-bis(diphenylthiophosphoramino)-1,2-cyclohexane 以 甲苯 为溶剂， 反应 6.0h， 以95%的产率得到
  参考文献：
  名称：

  高活性双核钛（IV）配合物催化碳-杂原子键的形成

  摘要：

  一系列单核钛（IV）与一般组合物的复合物κ 3 - [R {NHPh基2 P（X）} 2的Ti（NME 2）2 ] [R = C ^ 6 ħ 4，X = SE（图3b）; R =反式-C 6 ħ 10，X = S（图4a），硒（4B）]和[{κ 2 -N（PPH 2 Se）的2 } 2的Ti（NME 2）2 ]（图6b）和两个双核钛（IV）配合物，[C 6 H 4 {（NPh 2PS）（N）}的Ti（NME 2）] 2（图3c）和κ[{ 2 -N PPH（2 Se）中的Ti}（NME 2）2 ] 2（图6C）被报告。双核钛（IV）配合物6c在温和条件下可作为化学选择性将E–H键（E = N，O，S，P，C）加成到杂多烯中的有效催化剂。将脂肪族和芳香族胺，醇，硫醇，氧化膦和乙炔催化加成到碳二亚胺上，可以在温和的条件下以高收率高产率地得到相应的加氢产物。双核络合物的催化效率取决于Ti的协同作用

  DOI：

  10.1021/acs.inorgchem.8b01766
• 作为产物：
  描述：

  氯化二苯基硫磷 、 (1R,2R)-1,2-diaminocyclohexane 在 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以92%的产率得到(R,R)-bis(diphenylthiophosphoramino)-1,2-cyclohexane
  参考文献：
  名称：

  C2-Symmetric diphenylphosphoramide and diphenylthiophosphoramide derived from (1R,2R)-1,2-diaminocyclohexane as ligands for the titanium(IV) alkoxide-promoted addition of diethylzinc to aldehydes

  摘要：

  Chiral C-2-symmetric diphenylphosphoramide 4 and diphenylthiophosphoramide 5 were prepared from the reaction of diphenylphosphinic chloride and diphenylthiophosphinic chloride with (1R,2R)-(-)-1,2-diaminocyclohexane in the presence of diisopropylethylamine in high yields. They were used as chiral ligands in the catalytic asymmetric addition reaction of diethylzinc to aldehydes in the presence of titanium(IV) isopropoxide to give the corresponding sec-alcohols in 70-83% ee with an (R)-configuration and in 40-50% ee with an (S)-configuration, respectively. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(99)00348-1
• 作为试剂：
  描述：

  顺-环辛烯 在 (R,R)-bis(diphenylthiophosphoramino)-1,2-cyclohexane 作用下， 以 正戊烷 为溶剂， 反应 16.0h， 生成 反式环辛烯 、 反式环辛烯
  参考文献：
  名称：

  摘要：

  The optically active C-2-symmetric phosphoramides (2) and (3) were employed as chiral sensitizers for the geometrical photoisomerization of (Z)-cyclooctene (1Z) in pentane at varying temperatures. At low temperature (-56 degreesC), the achieved enantiomeric excesses (e.e.) for (1Z) are 20 and 28%, respectively.

  DOI：

  10.1071/ch01020

文献信息

• C2-Symmetric diphenylphosphoramide and diphenylthiophosphoramide derived from (1R,2R)-1,2-diaminocyclohexane as ligands for the titanium(IV) alkoxide-promoted addition of diethylzinc to aldehydes
  作者：Min Shi、Wen-Sheng Sui

  DOI：10.1016/s0957-4166(99)00348-1

  日期：1999.8

  Chiral C-2-symmetric diphenylphosphoramide 4 and diphenylthiophosphoramide 5 were prepared from the reaction of diphenylphosphinic chloride and diphenylthiophosphinic chloride with (1R,2R)-(-)-1,2-diaminocyclohexane in the presence of diisopropylethylamine in high yields. They were used as chiral ligands in the catalytic asymmetric addition reaction of diethylzinc to aldehydes in the presence of titanium(IV) isopropoxide to give the corresponding sec-alcohols in 70-83% ee with an (R)-configuration and in 40-50% ee with an (S)-configuration, respectively. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Synthesis, structure, and catalytic activity of titanium complexes with new chiral 11,12-diamino-9,10-dihydro-9,10-ethanoanthracene-based ligands
  作者：Furen Zhang、Haibin Song、Guofu Zi

  DOI：10.1016/j.jorganchem.2010.05.003

  日期：2010.8

  A new series of organo-titanium complexes have been prepared from the reaction between Ti(NMe2)(4) and C-2-symmetric ligands, (R,R)-11,12-bis(pyrrol-2-ylmethyleneamino)-9,10-dihydro-9,10-ethanoanthracene (1H(2)), and (R, R)-bis(diphenylthiophosphoramino)-9,10-dihydro-9,10-ethanoanthracene (2H(2)), (R,R)-11,12-bis(mesitylenesulphonylamino)-9,10-dihydro-9,10-ethanoanthracene (3H(2)) and (R,R)-bis (diphenylthiophosphoramino)-1,2-cyclohexane (4H(2)). Treatment of Ti(NMe2)(4) with 1 equiv of 1H(2) gives, after recrystallization from a benzene solution, the binuclear double helicate titanium amide (1) 2[ Ti (NMe2)(2)](2)center dot(5) in 71% yield. While under similar reaction conditions, reaction of Ti(NMe2)(4) with 1 equiv of 2H(2), 3H(2) or 4H(2) gives, after recrystallization from a toluene or benzene solution, the mononuclear single helicate titanium amides (2) Ti(NMe2)(2) (6), (3) Ti(NMe2)(2) (7) and (4) Ti(NMe2)(2) (8), respectively, in good yields. All new compounds have been characterized by various spectroscopic techniques, and elemental analyses. The solid-state structures of complexes 5-8 have further been confirmed by X-ray diffraction analyses. The titanium amides are active catalysts for the polymerization of rac-lactide, leading to the isotactic-rich polylactides. (C) 2010 Elsevier B.V. All rights reserved.
• Highly Active Dinuclear Titanium(IV) Complexes for the Catalytic Formation of a Carbon–Heteroatom Bond
  作者：Jayeeta Bhattacharjee、Adimulam Harinath、Indrani Banerjee、Hari Pada Nayek、Tarun K. Panda

  DOI：10.1021/acs.inorgchem.8b01766

  日期：2018.10.15

  The catalytic efficiency of the dinuclear complex depends on the cooperative effect of the TiIV ions, the systematic variation of the intermetallic distance, and the ligand’s steric properties of the complex, which enhances the reaction rate. Most interestingly, this is the first example of catalytic insertion of various E–H bonds into the carbodiimides using a single-site catalyst because only the titanium-mediated

  一系列单核钛（IV）与一般组合物的复合物κ 3 - [R NHPh基2 P（X）} 2的Ti（NME 2）2 ] [R = C ^ 6 ħ 4，X = SE（图3b）; R =反式-C 6 ħ 10，X = S（图4a），硒（4B）]和[κ 2 -N（PPH 2 Se）的2 } 2的Ti（NME 2）2 ]（图6b）和两个双核钛（IV）配合物，[C 6 H 4 （NPh 2PS）（N）}的Ti（NME 2）] 2（图3c）和κ[ 2 -N PPH（2 Se）中的Ti}（NME 2）2 ] 2（图6C）被报告。双核钛（IV）配合物6c在温和条件下可作为化学选择性将E–H键（E = N，O，S，P，C）加成到杂多烯中的有效催化剂。将脂肪族和芳香族胺，醇，硫醇，氧化膦和乙炔催化加成到碳二亚胺上，可以在温和的条件下以高收率高产率地得到相应的加氢产物。双核络合物的催化效率取决于Ti的协同作用
• ——
  作者：Min Shi、Yoshihisa Inoue

  DOI：10.1071/ch01020

  日期：——

  The optically active C-2-symmetric phosphoramides (2) and (3) were employed as chiral sensitizers for the geometrical photoisomerization of (Z)-cyclooctene (1Z) in pentane at varying temperatures. At low temperature (-56 degreesC), the achieved enantiomeric excesses (e.e.) for (1Z) are 20 and 28%, respectively.