(+)-N,N'-bis-(S)-α-methylbenzyl-1,2-diaminobenzene | 291545-05-6

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (+)-N,N'-bis-(S)-α-methylbenzyl-1,2-diaminobenzene
• 英文别名: 1-N,2-N-bis[(1S)-1-phenylethyl]benzene-1,2-diamine
• CAS: 291545-05-6
• 化学式: C₂₂H₂₄N₂
• 分子量: 316.446
• InChiKey: NSYLLZSQFNSKDN-ROUUACIJSA-N

物化性质

• 沸点：
  458.2±25.0 °C(Predicted)
• 密度：
  1.113±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.18
• 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：

  (+)-N,N'-bis-(S)-α-methylbenzyl-1,2-diaminobenzene 在 氯化亚砜 作用下， 以 乙醚 为溶剂， 反应 18.0h， 以30%的产率得到1,3-bis[(1S)-1-phenylethyl]-2lambda4,1,3-benzothiadiazole 2-oxide
  参考文献：
  名称：

  The first enantiomerically pure thiadiazol-3-one 1-oxide and thiatriaza-indene 3-oxide systems chiral at the sulfur atom

  摘要：

  The first synthesis of an enantiomerically pure C-2 symmetric benzothiadiazole 2-oxide is described along with the first synthesis of an enantiomerically thiadiazol-3-one 1-oxide and a thiatriaza-indene 3-oxide system both chiral at the sulfur atom. Excellent levels of diastereoselectivity were observed in the SO installation step, that is, the reaction of the prerequisite bis-amines with thionyl chloride at ambient temperature. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2010.07.025
• 作为产物：
  描述：

  1,2-二溴苯 在 tris-(dibenzylideneacetone)dipalladium(0) 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 、 sodium t-butanolate 作用下， 以 甲苯 为溶剂， 反应 49.5h， 生成 (+)-N,N'-bis-(S)-α-methylbenzyl-1,2-diaminobenzene
  参考文献：
  名称：

  A Versatile Synthesis of Substituted Benzimidazolium Salts by an Amination/Ring Closure Sequence

  摘要：

  [GRAPHICS]A new method to produce benzimidazolium salts based on a successive Buchwald-Hartwig amination and ring closure is reported. A variety of different benzimidazolium salts can be prepared using this procedure. Amines that bear an alpha -chiral group undergo the reaction to furnish chiral benzimidazolium salts. The salts that lack a C2 substituent on the heterocycle are readily deprotonated to give nucleophilic carbenes.

  DOI：

  10.1021/ol016254m

文献信息

• Synthesis of C2-Symmetric Benzimidazolium Salts and Their Application in Palladium-Catalyzed Enantioselective Intramolecular α-Arylation of Amides
  作者：Weiping He、Wei Zhao、Bihui Zhou、Haifeng Liu、Xiangrong Li、Linlin Li、Jie Li、Jianyou Shi

  DOI：10.3390/molecules21060742

  日期：——

  A series of C₂-symmetric chiral benzimidazolium salts, the precursor of N-heterocyclic carbene ligands, were designed and synthesized from 1,2-dibromobenzene. In situ prepared corresponding carbenes were tested in the asymmetric palladium-catalyzed intramolecular α-arylation of amides, affording chiral diarylmethanols with high yields and moderate enantioselectivities.

  由1,2-二溴苯设计并合成了一系列C 2对称的手性苯并咪唑鎓盐，它们是N-杂环卡宾配体的前体。在酰胺的不对称钯催化的分子内α-芳基化反应中测试了原位制备的相应碳烯，提供了高收率和中等对映选择性的手性二芳基甲醇。
• Synthesis of chiral N,N′-disubstituted 1,2-benzenediamines from o-dibromobenzene
  作者：Felix M Rivas、Uzma Riaz、Steven T Diver

  DOI：10.1016/s0957-4166(00)00124-5

  日期：2000.5

  Palladium-catalyzed amination of o-dibromobenzene provided chiral N,N'-disubstituted 1,2-benzenediamines in good to excellent yields. The amination was executed stepwise and in one pot to give unsymmetrically and symmetrically substituted 1,2-benzenediamines. Incorporation of chiral primary amines was possible without racemization using catalytic Pd(2)dba(3)-BINAP. (C) 2000 Elsevier Science Ltd. All rights reserved.
• A new paradigm in N-heterocyclic carbenoid ligands
  作者：Philip C. Bulman Page、Benjamin R. Buckley、Steven D.R. Christie、Mark Edgar、Andrew M. Poulton、Mark R.J. Elsegood、Vickie McKee

  DOI：10.1016/j.jorganchem.2005.09.015

  日期：2005.12

  We report a new class of very readily prepared chiral N-heterocyclic carbenoid ligand that also contains two different types of chirality: an asymmetric centre and an atropoisomeric unit, but contained in two separate N-substituents, such that both can easily be varied. In addition to its simplicity and flexibility, this approach has potential advantages over systems containing only atropoisomeric units, because the inclusion of an additional fixed asymmetric centre means that the atropoisomers are diastereoisomers and therefore chemically distinct entities. Complexation to a metal centre increases the barrier to rotation in the atropoisomeric unit so that the two diastercoisomers may be separable by simple methods such as standard chromatography. In addition, a novel cis-substituted palladium complex has been characterised by X-ray crystallography. (c) 2005 Elsevier B.V. All rights reserved.
• Removal of Palladium from Cross-Coupling Reactions Using Isocyanide Reagents
  作者：Jonathan M. French、Justin R. Griffiths、Steven T. Diver

  DOI：10.1002/adsc.201400754

  日期：2015.2.9

  AbstractIsocyanide reagents removed residual palladium from palladium‐catalyzed cross‐couplings, to sub‐ppm levels. The results were similar using either Pd(II) or Pd(0) precatalysts. Using the 3‐isocyanopropylated silica gel reagent 1, no chromatography or other treatments were required. The soluble isocyanide potassium isocyanoacetate (KO2CCH2NC) was also found to be highly effective when combined with silica gel chromatography.magnified image