4,5-diphenylethylene (cis,trans) sulphate

• 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: 4,5-diphenylethylene (cis,trans) sulphate
• 英文别名: (4R,5R)-4,5-diphenyl-1,3,2-dioxathiolane 2,2-dioxide
• 化学式: C₁₄H₁₂O₄S
• 分子量: 276.313
• InChiKey: ZRHYPUWGNKZMRW-ZIAGYGMSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  61
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4,5-diphenylethylene (cis,trans) sulphate 在 lithium iodide 作用下， 以 丙酮 为溶剂， 反应 0.5h， 以95%的产率得到反式-1,2-二苯乙烯
  参考文献：
  名称：

  A Convenient Method for Olefination of vic-Diols by Lithium Iodide via Cyclic Sulfates

  摘要：

  vic-二醇的环状硫酸酯与碘化锂在丙酮中反应，在低温下以优异的分离产率产生相应的烯烃。反式二醇的环状硫酸酯专门生成反式烯烃。顺式二醇的环状硫酸酯得到顺式和反式烯烃的混合物。该反应条件温和，后处理程序简单。

  DOI：

  10.1055/s-1997-782
• 作为产物：
  描述：

  (R,R)-(+)-4,5-diphenyl-1,3,2-dioxathiolan-2-one 在 ruthenium trichloride 、 sodium periodate 作用下， 以 四氯化碳 、 乙腈 为溶剂， 反应 1.0h， 生成 4,5-diphenylethylene (cis,trans) sulphate
  参考文献：
  名称：

  Conformational Preferences of RNase A C-Peptide Derivatives Containing a Highly Constrained Analogue of Phenylalanine

  摘要：

  Both enantiomers of a highly constrained derivative of phenylalanine, FiFi, were prepared in optically pure form. Studies were performed to elucidate the effects of substituting this amino acid for phenylalanine in RN-24, a derivative of the RNase A C-peptide. Thus RN-24, and the analogues 9 and 10, in which Phe-8 was replaced by each of the enantiomers of FiFi, were prepared. Comparative circular dichroism (CD) experiments indicated relative tendencies to adopt helical structures, and variable-temperature CD studies showed the relative ease with which these conformations were lost at elevated temperatures. These observations were rationalized via computer-assisted molecular modeling, which showed that the phenyl groups of (R,R)-FiFi in the peptidomimetic 9 can be accommodated via distortion of the helical conformations and that such distorted conformations persist as the temperature is increased. Conversely, intolerable contacts occur in an analogous conformation of the (S,S)-FiFi peptidomimetic 10 and these preclude helicity. Consistent with these observations, molecular dynamics studies of these peptidomimetics at 276 K indicate that helical conformations of 9 and RN-24 are observable under conditions in which the analogous conformation of 10 is lost. Overall, these studies demonstrate that cyclopropane amino acids can be used to enforce elements of secondary structure (albeit distorted) or to preclude them altogether.

  DOI：

  10.1021/ja981153d

文献信息

• Solvent- and Temperature-Dependent Functionalisation of Enantioenriched Aziridines
  作者：Maria Carolina de Ceglie、Biagia Musio、Francesco Affortunato、Anna Moliterni、Angela Altomare、Saverio Florio、Renzo Luisi

  DOI：10.1002/chem.201002172

  日期：2011.1.3

  for the synthesis of chiral tri‐substituted aziridines with different stereochemistry. In contrast, chiral aziridine (S,S)‐1 c showed a temperature‐dependent reactivity to give chiral ortho‐lithiated aziridine 1 c‐ortho‐Li at −78 °C and α‐lithiated aziridine 1 c‐α‐Li at 0 °C. Both lithiated intermediates react with electrophiles to give enantioenriched ortho‐ and α‐functionalised aziridines. The reaction

  据报道，手性非外消旋氮丙啶具有高度立体选择性和区域选择性功能。通过从母体对映体富集的氮丙啶开始并精细调节反应条件，可以解决锂化/亲电子捕获序列的区域选择性和立体选择性，从而可以制备高度对映体的官能化氮丙啶。从手性Ñ烷基反式-2,3- diphenylaziridines（小号，小号） - 1，b中，两个不同构造的手性aziridinyllithiums可以产生（反式- 1，B-锂在甲苯中，顺式- 1一，b-Li在THF中），因此揭示了溶剂依赖的反应性，可用于合成具有不同立体化学的手性三取代氮丙啶。相比之下，手性氮丙啶（S，S）-1 c表现出温度依赖性，可在-78°C时得到手性邻甲硅烷基化的氮丙啶1 c-邻-Li，在0 ℃时得到α-锂化的氮丙啶1c-α-Li ℃。两种锂化中间体均与亲电试剂反应生成对映体富集的邻位-和α-官能化的氮丙啶。的反应的所有锂化氮丙啶与羰基化合物布置有用的手性羟烷基化
• A Convenient Method for Olefination of <i>vic</i>-Diols by Lithium Iodide <i>via</i> Cyclic Sulfates
  作者：Doo Jang、Yung Joo

  DOI：10.1055/s-1997-782

  日期：1997.3

  Reaction of cyclic sulfates of vic-diols with lithium iodide in acetone produced the corresponding olefins in excellent isolated yields at low temperature. Cyclic sulfates of trans-diols gave trans-alkenes exclusively. Cyclic sulfates of cis-diols gave a mixture of cis- and trans-alkenes. The reaction offers mild conditions and easy work-up procedures.

  vic-二醇的环状硫酸酯与碘化锂在丙酮中反应，在低温下以优异的分离产率产生相应的烯烃。反式二醇的环状硫酸酯专门生成反式烯烃。顺式二醇的环状硫酸酯得到顺式和反式烯烃的混合物。该反应条件温和，后处理程序简单。
• Use of Optically Active Cyclic <i>N</i>,<i>N</i>-Dialkyl Aminals in Asymmetric Induction
  作者：Michael E. Jung、Adrian Huang

  DOI：10.1021/ol0001517

  日期：2000.8.1

  [reaction: see text]Cyclization of the optically active ketone N,N-dialkyl aminals A affords the diastereomer B as the major product with diastereoselectivities ranging from nearly 1:1 to essentially 100:0 depending on the cyclization studied.

  [反应：见正文]根据所研究的环化作用，旋光性酮N，N-二烷基缩醛胺A的环化提供了非对映异构体B作为主要产物，其非对映体选择性范围从接近1：1到基本上100：0。
• trans-(2R,3R)-2,3-Diphenylcyclopropane-1,1-dimethanol: a pivotal diol for the synthesis of novel C2-symmetric ligands for asymmetric transition metal catalysis
  作者：Elias Vervecken、Michel Van Overschelde、Timothy Noël、Yaşar Gök、Susana Alvárez Rodríguez、Simon Cogen、Johan Van der Eycken

  DOI：10.1016/j.tetasy.2010.08.007

  日期：2010.10

  Various chiral ligands bearing phosphorus or nitrogen donor atoms were obtained in a straightforward manner starting from trans-(2R,3R)-diphenylcyclopropane-1,1-dimethanol as a key structure. These chiral ligands were tested and compared in palladium(0)-catalyzed asymmetric allylic alkylation reactions (up to 71% ee) and rhodium(1)-catalyzed asymmetric hydrogenations (up to 88% ee). Moreover, in the asymmetric allylic alkylation, we observed excellent activity with a diphosphinite ligand (TOF = 600 mol 17 x [mol Pd x h)(-1)]. (C) 2010 Elsevier Ltd. All rights reserved.
• A Facile Route to Olefins from<i>Vic</i>-Diols<i>Via</i>Cyclic Sulfates with Triphenylphosphine and Iodine
  作者：Doo Ok Jang、Yung Hyup Joo、Dae Hyan Cho

  DOI：10.1080/00397919708004099

  日期：1997.7

  Treatment of cyclic sulfates of vic-diols with triphenylphosphine and iodine offers the corresponding olefins in high yields at room temperature. Both cyclic sulfates of d,l-hydrobenzoin and meso-hydrobenzoin give trans-stilbene.