(meso)-1,2-bis(phenylsulfinyl)ethane | 21461-90-5

• 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: (meso)-1,2-bis(phenylsulfinyl)ethane
• 英文别名: [(S)-2-[(R)-phenylsulfinyl]ethylsulfinyl]benzene
• CAS: 21461-90-5
• 化学式: C₁₄H₁₄O₂S₂
• 分子量: 278.396
• InChiKey: CSZMCUCIIIAHQD-HDICACEKSA-N

物化性质

• 熔点：
  166 °C
• 沸点：
  520.5±33.0 °C(Predicted)
• 密度：
  1.36±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  72.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  三苯基氯化锡 、 (meso)-1,2-bis(phenylsulfinyl)ethane 以 乙醇 为溶剂， 生成 (triphenyltin chloride)2 meso-bis(phenylsulfinyl)ethane
  参考文献：
  名称：

  三苯基氯化锡与双（苯基亚磺酰基）乙烷配合物的立体化学和晶体结构

  摘要：

  摘要2：1制备了三苯基氯化锡（TPTC）与内消旋-rac-双（苯基亚磺酰基）乙烷（meso，rac-BPSE）的配合物，其晶体形式适合于晶体学。复数（TPTC）2·meso-BPSE是单斜晶，a = 8.813（2），b = 22.920（5），c = 11.929（4）A，β= 104.16（2）°，空间群P21 / n。（TPTC）2·rac-BPSE与（TPTC）2·meso-BPSE是相同的络合物，并且当配体与TPTC反应时，rac-BPSE中的一个硫原子发生构型反转。

  DOI：

  10.1016/s0020-1693(00)84669-1
• 作为产物：
  描述：

  2-phenylethyl phenyl sulfoxide 在 2,2,6,6-tetramethyl-piperidine-N-oxyl 、 sodium hypochlorite 作用下， 以 二氯甲烷 、 水 为溶剂， 生成 (meso)-1,2-bis(phenylsulfinyl)ethane
  参考文献：
  名称：

  Facile Oxidation of Sulfides to Sulfoxides using Sodium Hypochlorite and Oxoammonium Salt as a Catalyst: Chemo- and Diastereoselective Transformation of Bis(phenylthio)alkanes into Sulfoxides

  摘要：

  本文介绍了一种简便且具有选择性的方法来进行上述转化。在 TEMPO 的介导以及溴化钾和四氯化碳的共同催化下，二硫化物与一或两个当量的次氯酸钠发生两相氧化反应，分别生成相应的一硫醚或二硫醚。在 1,2- 1,3-双（苯硫基）烷烃和正交双（苯硫基甲基）苯的情况下，可生成相应的中二硫醚，非对映选择性为 90-98%。

  DOI：

  10.1055/s-1994-25486
• 作为试剂：
  描述：

  pent-4-enyl 4-nitrophenylsulfonylcarbamate 在 Pd[1,2-bis(phenylsulfinyl)ethane](OAc)2 、 (meso)-1,2-bis(phenylsulfinyl)ethane 、 氧气 、 苯基-P-苯醌 、 对硝基苯甲酸 作用下， 以 1,2-二氯乙烷 为溶剂， 以72%的产率得到(+/-)-3-(4-nitrophenylsulfonyl)-4-vinyl-1,3-oxazinan-2-one
  参考文献：
  名称：

  Allylic C−H Amination for the Preparation of syn-1,3-Amino Alcohol Motifs

  摘要：

  A highly selective and general Pd/sulfoxide-catalyzed allylic C-H amination reaction en route to syn-1,3-amino alcohol motifs is reported. Key to achieving this reactivity under mild conditions is the use of electron-deficient N-nosyl carbamate nucleophiles that are thought to promote functionalization by furnishing higher concentrations of anionic species in situ. The reaction is shown to be orthogonal to classical C-C bond-forming/-reduction sequences as well as nitrene-based C-H amination methods.

  DOI：

  10.1021/ja9054959

文献信息

• Catalytic Enantioselective Oxidation of Bulky Alkyl Aryl Thioethers with H2O2 over Titanium-Salan Catalysts
  作者：Konstantin P. Bryliakov、Evgenii P. Talsi

  DOI：10.1002/ejoc.201100557

  日期：2011.8

  procedure for the oxidation of bulky (preferably aryl benzyl substituted) thioethers with hydrogen peroxide in good to high yields and enantioselectivities (up to 98.5 % ee) is reported. The high optical yields are achieved in a tandem stereoconvergent enantioselective oxidation and kinetic resolution process. A reasonable balance between the sulfoxide yield and enantioselectivity could be found by varying

  报道了一种用过氧化氢以良好至高产率和对映选择性（高达 98.5% ee）氧化大体积（优选芳基苄基取代）硫醚的简单有效的催化程序。在串联立体会聚对映选择性氧化和动力学拆分过程中实现了高光学产率。通过改变浓度和温度可以找到亚砜产率和对映选择性之间的合理平衡。报道了用于制备更具立体选择性的催化剂的钛-salan 催化剂的改进合成。
• Sulfoxide ligand metal catalyzed oxidation of olefins
  申请人：The Board of Trustees of the University of Illinois

  公开号：US10266503B1

  公开（公告）日：2019-04-23

  The enantioselective synthesis of isochroman motifs has been accomplished via Pd(II)-catalyzed allylic C—H oxidation from terminal olefin precursors. Critical to the success of this goal was the development and utilization of a novel chiral aryl sulfoxide-oxazoline (ArSOX) ligand. The allylic C—H oxidation reaction proceeds with the broadest scope and highest levels asymmetric induction reported to date (avg. 92% ee, 13 examples ≥90% ee). Additionally, C(sp3)-N fragment coupling reaction between abundant terminal olefins and N-triflyl protected aliphatic and aromatic amines via Pd(II)/sulfoxide (SOX) catalyzed intermolecular allylic C—H amination is disclosed. A range of 52 allylic amines are furnished in good yields (avg. 76%) and excellent regio- and stereoselectivity (avg. >20:1 linear:branched, >20:1 E:Z). For the first time, a variety of singly activated aromatic and aliphatic nitrogen nucleophiles, including ones with stereochemical elements, can be used in fragment coupling stiochiometries for intermolecular C—H amination reactions.

  通过Pd(II)-催化的烯烃末端前体的烯丙基C—H氧化，已经实现了对异色烷基苯并环的对映选择性合成。这一目标的成功关键在于开发和利用一种新型手性芳基亚砜-噁唑啉（ArSOX）配体。烯丙基C—H氧化反应具有迄今报道的最广泛范围和最高水平的不对称诱导（平均92% ee，13个例子≥90% ee）。此外，通过Pd(II)/亚砜（SOX）催化的分子间烯丙基C—H胺化揭示了丰富的末端烯烃和N-三氟甲磺酰保护的脂肪族和芳香族胺之间的C(sp3)-N片段偶联反应。一系列52种烯丙基胺以良好的产率（平均76%）和优异的区域和立体选择性（平均>20:1线性:支链，>20:1 E:Z）提供。首次，各种单独活化的芳香族和脂肪族氮亲核试剂，包括具有立体化学元素的试剂，可以在分子间C—H胺化反应的片段偶联化学计量中使用。
• Serial Ligand Catalysis:  A Highly Selective Allylic C−H Oxidation
  作者：Mark S. Chen、Prabagaran Narayanasamy、Nathan A. Labenz、M. Christina White

  DOI：10.1021/ja0500198

  日期：2005.5.18

  We are reporting a mild, chemo-, and highly regioselective Pd(II)-catalyzed allylic oxidation of alpha-olefins to furnish branched allylic esters that proceeds via a novel serial ligand catalysis mechanism in which two different ligands (i.e., vinyl sulfoxide 2 and BQ) interact sequentially with the metal to promote distinct steps of the catalytic cycle (i.e., C-H cleavage and pi-allyl functionalization

  我们正在报告一种温和的、化学的和高度区域选择性的 Pd(II) 催化的 α-烯烃烯丙基氧化，以提供支链烯丙基酯，该反应通过一种新型的串联配体催化机制进行，其中两种不同的配体（即乙烯基亚砜 2 和BQ) 依次与金属相互作用以促进催化循环的不同步骤（即分别为 CH 裂解和 pi-烯丙基功能化）。
• Synthesis of C3- and C2-symmetric tris- and bis-sulfoxide ligands by asymmetric oxidation
  作者：Peter K. Dornan、Priscilla L. Leung、Vy M. Dong

  DOI：10.1016/j.tet.2011.02.023

  日期：2011.6

  A series of tris- and bis-sulfoxides were synthesized by multiple asymmetric oxidation of the corresponding sulfides. High enantioselectivities were obtained based on Horeau-type amplification of selectivity. Naphthyl-substituted sulfoxides allowed for higher selectivity and greater ease of purification. These sulfoxides were tested as ligands in rhodium-catalyzed olefin hydroacylation and 1,4-addition of phenyl boronic acid to 2-cyclohexen-1-one. While no enantioinduction was observed in hydroacylation, up to 80% ee was obtained for a tris-sulfoxide and a bis-sulfoxide ligand in the 1,4-addition. Bis-sulfoxides with flexible backbones gave lower and inversed enantioselectivity, suggesting backbone rigidity plays a key role in enantioinduction. (C) 2011 Elsevier Ltd. All rights reserved.
• Vanadium catalyzed enantioselective oxidation of sulfides: easy transformation of bis(arylthio)alkanes into C2 symmetric chiral sulfoxides
  作者：Jacek Skarżewski、Elżbieta Ostrycharz、Renata Siedlecka

  DOI：10.1016/s0957-4166(99)00374-2

  日期：1999.9

  A facile and selective method for the title transformation is described. The two-phase oxidation of bis-sulfides with hydrogen peroxide catalyzed by vanadium complex of chiral Schiff base leads to the corresponding chiral mono- and bis-sulfoxides. In the case of 1,2-bis(arylthio)ethanes the respective optically active bis-sulfoxides are formed in up to over 95% e.e. (C) 1999 Elsevier Science Ltd. All rights reserved.