(1S,2S)-1,2-diphenyl-N¹,N²-bis(mesitylmethyl)ethane-1,2-diamine | 124070-54-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: (1S,2S)-1,2-diphenyl-N¹,N²-bis(mesitylmethyl)ethane-1,2-diamine
• 英文别名: (1S,2S)-(-)-1,2-di(2,4,6-trimethylbenzylamino)-1,2-diphenylethane；(S,S)-N,N'-bis(mesitylmethyl)-1,2-diphenyl-1,2-ethanediamine；(S,S)-(Me3C6H2CH2NHCH(Ph))2；(S,s)-(-)-1,2-di(2,4,6-trimethylbenzylamino)-1,2-diphenylethane；(1S,2S)-1,2-diphenyl-N,N'-bis[(2,4,6-trimethylphenyl)methyl]ethane-1,2-diamine
• CAS: 124070-54-8
• 化学式: C₃₄H₄₀N₂
• 分子量: 476.705
• InChiKey: NIAVGNITXGZNAA-HEVIKAOCSA-N

物化性质

• 熔点：
  135-136 °C(Solv: ethanol (64-17-5))
• 沸点：
  611.0±50.0 °C(Predicted)
• 密度：
  1.049±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.6
• 重原子数：
  36
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  24.1
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  甲基二氯膦 、 (1S,2S)-1,2-diphenyl-N¹,N²-bis(mesitylmethyl)ethane-1,2-diamine 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 以65%的产率得到(4S,5S)-2-methyl-4,5-diphenyl-1,3-bis[(2,4,6-trimethylphenyl)methyl]-1,3,2-diazaphospholidine
  参考文献：
  名称：

  Enantioselective conjugate addition of diethylzinc to cyclohexenone catalyzed by a chiral aminophosphine–copper(II) triflate

  摘要：

  Enantioselective conjugate addition of diethylzinc to cyclohexenone and 4,4-dimethylcyclohexenone was catalyzed by the combination of 0.1 equiv. of a chiral monodentate aminophosphine 3 and 0.05 equiv. of copper(If) triflate to give the corresponding adducts 4 in up to 70% ee. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(98)00348-6
• 作为产物：
  描述：

  2,4,6-三甲基苯甲醛 在 sodium tetrahydroborate 、 三乙胺 作用下， 以 乙醇 为溶剂， 反应 24.0h， 生成 (1S,2S)-1,2-diphenyl-N¹,N²-bis(mesitylmethyl)ethane-1,2-diamine
  参考文献：
  名称：

  用于烯烃对映选择性二羟基化的 Corey 手性控制剂的制备合成

  摘要：

  1,2-二(2,4,6-三甲基苄基氨基)-1,2-二苯基乙烷的两种对映异构体的五步合成，即用于对映选择性二羟基化的 Corey (R,R)- 和 (S,S)- 控制器已经开发出以 α,α'-二苯基乙醛肟为原料的四氧化锇制备烯烃的方法。合成中的关键操作是仅使用 (R,R)-酒石酸将中间体 1,2-二氨基-1,2-二苯基乙烷光学拆分为两种对映异构体，随后将对映异构体纯度提高至 >98%相应希夫双碱的结晶。使用控制器与 (R)-α-甲氧基-α-(三氟甲基)苯乙酸 (MosherR-酸) 盐的 1 H NMR 光谱可以轻松地分析控制器的对映体纯度。

  DOI：

  10.1007/bf02495355
• 作为试剂：
  描述：

  (3R,3aR,5S,6R,7S,8S,8aS)-5-(methoxymethoxymethyl)-3,7-dimethyl-8-phenylmethoxy-6-tri(propan-2-yl)silyloxy-2,3,3a,5,6,7,8,8a-octahydrofuro[3,2-b]oxepin-2-ol 在 4-二甲氨基吡啶 、 四氧化锇 、 重铬酸吡啶 、 pyridine-SO3 complex 、 二甲基硫 、 4 A molecular sieve 、 camphor-10-sulfonic acid 、 三氟化硼乙醚 、 sodium hexamethyldisilazane 、 4-甲基苯磺酸吡啶 、 sodium hydride 、 溶剂黄146 、 (1S,2S)-1,2-diphenyl-N¹,N²-bis(mesitylmethyl)ethane-1,2-diamine 、 三乙胺 、 9-硼双环[3.3.1]壬烷 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 、 水 、 二甲基亚砜 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 50.58h， 生成 [(2R,3S,4S,4'S,4aR,6S,7R,8R,9S,9aS)-7-hydroxy-3,4,8-trimethyl-4',9-bis(phenylmethoxy)spiro[3,4,4a,6,7,8,9,9a-octahydropyrano[3,2-b]oxepine-2,2'-oxolane]-6-yl]methyl 4-methylbenzenesulfonate
  参考文献：
  名称：

  Stereocontrolled Synthesis of the JKLM Ring Fragment of Ciguatoxin

  摘要：

  A highly stereocontrolled synthesis of the JKLM ring fragment of ciguatoxin has been achieved. The present synthesis starts with methyl 4,6-O-benzylidene-2-deoxy-2-C-methyl-a-D whose configurations and substituents at C2-C5 correspond to those at C46-C49 of ciguatoxin, and involves as the key step base-induced 7-endo selective cyclization of a hydroxy epoxide for the efficient construction of the fully substituted oxepane ring K. Construction of the spiroether ring M was achieved by introduction of an allyl group to the ring L lactone followed by asymmetric dihydroxylation to install the C54 stereogenic center and acid-induced spiroketalization to furnish the protected KLM ring system. Finally, ring J was constructed by the method of Nicolaou to complete the synthesis of the JKLM ring fragment. The synthesis of a carboxylic acid derivative and its conjugation to carrier proteins to give an artificial antigen for development of an immunoassay system for the parent toxin molecule are also reported.

  DOI：

  10.1021/jo990988j

文献信息

• Enantioselective vicinal hydroxylation of terminal and E-1,2-disubstituted olefins by a chiral complex of osmium tetroxide. An effective controller system and a rational mechanistic model
  作者：E. J. Corey、Paul DaSilva Jardine、Scott Virgil、Po Wai Yuen、Richard D. Connell

  DOI：10.1021/ja00208a025

  日期：1989.12

  The suprafacial hydroxylation of olefins by osmium tetraoxide, though a much used synthetic method, would become even more important if three conditions could be met: (1) modification to achieve high and predictable enantioselectivity and acyclic diastereoselectivity, (2) clarification of reaction mechanism, and (3) facilitated recovery and recycling of osmium. This paper reports progress on all three

  四氧化锇表面羟基化烯烃虽然是一种常用的合成方法，但如果满足三个条件，则将变得更加重要：（1）改性以实现高且可预测的对映选择性和非环非对映选择性，（2）阐明反应机理， (3)促进锇的回收和再循环。本文报告了所有三个方面的进展。
• <i>C</i>₂ Symmetric Chiral NHC Ligand for Asymmetric Quaternary Carbon Constructing Copper-Catalyzed Conjugate Addition of Grignard Reagents to 3-Substituted Cyclohexenones
  作者：Yasumasa Matsumoto、Ken-ichi Yamada、Kiyoshi Tomioka

  DOI：10.1021/jo800613h

  日期：2008.6.1

  The asymmetric construction of quaternary carbon centers by conjugate addition of Grignard reagents to 3-methyl- and 3-ethylcyclohexenones was realized in a maximum enantioselectivity of 80% by using a C2 symmetric chiral N-heterocyclic carbene (NHC)-copper catalyst, generated from (4S,5S)-1,3-bis(2-methoxyphenyl)-4,5-diphenyl-4,5-dihydro-1H-imidazol-3-ium tetrafluoroborate and copper(II) triflate

  通过使用生成的C 2对称手性N-杂环卡宾（NHC）-铜催化剂，通过将格氏试剂共轭添加到3-甲基和3-乙基环己酮中来实现季碳中心的不对称构建，其最大对映体选择性为80％。（4S，5S）-1，3-双（2-甲氧基苯基）-4，5-二苯基-4，5-二氢-1H-咪唑-3-四氟硼酸钾和三氟甲磺酸铜（II）。通过X射线晶体学分析了NHC-Au配合物的立体结构，合理化了N-芳基NHCs的良好立体控制能力。
• Efficient syntheses of four stable-isotope labeled (1R)-menthyl (1S,2S)-(+)-2-phenylcyclopropanecarboxylates
  作者：Edmund J. Keliher、Richard C. Burrell、Harry R. Chobanian、Karina L. Conkrite、Rajesh Shukla、John E. Baldwin

  DOI：10.1039/b605912k

  日期：——

  Many carbenoid cyclopropanation reactions promoted by chiral catalysts give product mixtures reflecting impressive diastereo- and enantioselectivities. Few provide a single chiral product efficiently. This limitation has been overcome in cyclopropanations of styrene and isotopically labeled styrenes with α-diazoacetates. Convenient syntheses on a 20 g scale of each of four chiral isotopically labeled (1R)-menthyl (1S,2S)-2-phenylcyclopropanecarboxylates (the 1-d-3-13C, 1,(3S)-d2, 1,2,(3S)-d3, and 1,3,3-d3 isotopomers) of better than 99% ee have been realized.

  许多由手性催化剂促进的类卡宾环丙烯化反应产生的产物混合物显示出令人印象深刻的非对称选择性和针对性的选择性。但很少有反应能高效地产生单一的手性产物。这一限制在与α-二氮杂乙酸酯的苯乙烯和同位素标记苯乙烯的环丙烯化反应中得到了克服。已经成功合成了四种手性同位素标记的(1R)-薄荷基(1S,2S)-2-苯基环丙烷羧酸酯（1-d-3-13C、1,(3S)-d2、1,2,(3S)-d3和1,3,3-d3同位素异构体），其对映体过量（ee）均超过99%。
• Chiral Recognition in Silver(I) Olefin Complexes with Chiral Diamines. Resolution of Racemic Alkenes and NMR Discrimination of Enantiomers
  作者：Maria E. Cucciolito、Germana Flores、Aldo Vitagliano

  DOI：10.1021/om0341653

  日期：2004.1.1

  The fragment [(chiral diamine)Ag]+ is a very useful reagent, both for the resolution of racemic alkenes and for the 1H or 13C NMR determination of the enantiomeric abundances of chiral olefinic compounds.

  片段[（手性二胺）Ag] +是非常有用的试剂，用于拆分外消旋烯烃以及用于1 H或13 C NMR测定手性烯烃化合物的对映体丰度。
• Chiral Diamine−Silver(I)−Alkene Complexes:  A Quantum Chemical and NMR Study
  作者：Elsa Kieken、Olaf Wiest、Paul Helquist、Maria E. Cucciolito、Germana Flores、Aldo Vitagliano、Per-Ola Norrby

  DOI：10.1021/om050275t

  日期：2005.7.1

  The ability of chiral diamine silver complexes to bind chiral and prochiral alkenes has been analyzed in detail. The stereoselectivity in binding of alkenes to a chiral ethanediamine silver complex has been investigated by NMR. The low-energy conformations of several small model complexes have been explored by DFT methods. By successive substitution of the computational model complexes, it has been possible to elucidate the role of each amine substituent in achieving successful discrimination of alkenes. The conformational space has been fully explored using small model systems, allowing an unbiased calculation of stereoselectivities that match well the experimental results. For a chiral allylic alcohol substrate, the correct stereoselectivity was obtained only when the structures were optimized with a continuum representation of the solvent. The discrepancy between gas phase and solution data is found to result from a competition between internal stabilization and solvation of the OH group of the substrate.