1,2-(R,R)-bis-benzenesulfinyl-ethane | 6099-21-4

• 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: 1,2-(R,R)-bis-benzenesulfinyl-ethane
• 英文别名: 1,2-Bis-((R)-benzolsulfinyl)-aethan；[(R)-2-[(R)-phenylsulfinyl]ethylsulfinyl]benzene
• CAS: 6099-21-4；21461-71-2；21461-90-5；27995-59-1；28045-36-5；60562-05-2
• 化学式: C₁₄H₁₄O₂S₂
• 分子量: 278.396
• InChiKey: CSZMCUCIIIAHQD-QZTJIDSGSA-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

安全信息

• 海关编码：
  2930909090

反应信息

• 作为产物：
  描述：

  在 sodium methylate 、 聚甘氨酸 作用下， 以 甲醇 为溶剂， 反应 2.0h， 以20%的产率得到1,2-(R,R)-bis-benzenesulfinyl-ethane
  参考文献：
  名称：

  Thermodynamic Resolution and Enantioselective Synthesis of C₂-Symmetric Bis-sulfoxides Based on Chiral Iridium(III) Complexes

  摘要：

  Enantiopure Λ-[Ir(dfppy)₂(MeCN)₂](PF₆) and Δ-[Ir(dfppy)₂(MeCN)₂](PF₆) (where dfppy is (4,6-difluoropheny)pyridine) were demonstrated to preferentially react with (S,S)-1,2-bis(arylsulfinyl)ethane and (R,R)-1,2-bis(arylsulfinyl)ethane, respectively, under thermodynamic equilibrium. Sequential treatment of Λ-[Ir(dfppy)₂(MeCN)₂](PF₆) and Δ-[Ir(dfppy)₂(MeCN)₂](PF₆) with C₂-symmetric bis-sulfoxides led to diastereoselective formation of the corresponding diastereomers Λ-[Ir(dfppy)₂(R,R)-bis-sulfoxide)](PF₆) in 90-92% and Δ-[Ir(dfppy)₂(S,S)-bis-sulfoxide)](PF₆) in 88-90%, respectively. The uncoordinated (R,S)-bis-sulfoxides were afforded in 45% with >97% de values. Enantiopure (S,S)-bis-sulfoxides and (R,R)-bis-sulfoxides were respectively obtained by the release of sulfoxide ligands from the corresponding complexes in the presence of glycine in yields of 20-21% with 97-99% ee values. The enantioreceptors Λ-[Ir(dfppy)₂(MeCN)₂](PF₆) and Δ-[Ir(dfppy)₂(MeCN)₂](PF₆) can be recycled and reused in the next reaction cycle. Moreover, a protocol for asymmetric oxidation of prochiral bis-sulfide into enantiopure C₂ symmetric bis-sulfoxide was also developed in a high enantioselectivity. The absolute configurations at the metal centers and sulfur atoms were determined by X-ray crystallography.

  DOI：

  10.1021/acs.inorgchem.9b01682
• 作为试剂：
  描述：

  2-环己烯-1-酮 、 苯硼酸 在 chlorobis(ethylene)rhodium(I) dimer 、 1,2-(R,R)-bis-benzenesulfinyl-ethane 、 potassium hydroxide 作用下， 以 乙酸乙酯 为溶剂， 反应 18.0h， 以82%的产率得到3-苯基环己酮
  参考文献：
  名称：

  Synthesis of C3- and C2-symmetric tris- and bis-sulfoxide ligands by asymmetric oxidation

  摘要：

  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.

  DOI：

  10.1016/j.tet.2011.02.023

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。
• 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）。
• 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
  作者：Renata Siedlecka、Jacek Skarżewski

  DOI：10.1055/s-1994-25486

  日期：——

  A facile and selective method for the title transformation is described. The two-phase oxidation of disulfides with one or two equivalents of sodium hypochlorite mediated by TEMPO and co-catalyzed by potassium bromide and PTC leads to the corresponding mono- or disulfoxides, respectively. In the case of 1,2- 1,3-bis(phenylthio)alkanes and ortho-bis(phenylthiomethyl)benzene the respective meso disulfoxides are formed in 90-98% diastereoselectivity.

  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%。
• 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.
• Synthetic Versatility in C–H Oxidation: A Rapid Approach to Differentiated Diols and Pyrans from Simple Olefins
  作者：Paul E. Gormisky、M. Christina White

  DOI：10.1021/ja206013j

  日期：2011.8.17

  Conventionally, C-H oxidation reactions are used to install functional groups. The use of C-H oxidation to transform simple starting materials into highly versatile intermediates, which enable rapid access to a range of complex target structures, is a new area with tremendous potential in synthesis. Herein we report a Pd(II)/sulfoxide-catalyzed allylic C-H oxidation to form anti-1,4-dioxan-2-ones from homoallylic oxygenates. These versatile building blocks are rapidly elaborated to differentiated syn-1,2-diols, stereo-defined amino-polyols, and syn-pyrans, structures ubiquitous in medicinally important complex molecules found in Nature. We also demonstrate that a C-H oxidation approach to the synthesis of these motifs is orthogonal and complementary to other state-of-the-art methods.