4,6-dimethyltrimethylene (cis,trans) sulphite | 29882-38-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧硫杂环戊烷
• 英文名称: 4,6-dimethyltrimethylene (cis,trans) sulphite
• 英文别名: cis-4, trans-6-dimethyl-r-2-oxo-1,3,2-dioxathiane；(4RS,6RS)-4,6-dimethyl-1,3,2-dioxathiane-2-oxide；trans-4,6-Dimethyl-2-oxo-1,3,2-dioxathian；dl-4.6-Dimethyl-trimethylensulfit；dl-4cis,6trans-Dimethyl-1,3-dioxa-2-thiacyclohexan-2ref-oxid；4r,6t-dimethyl-[1,3,2]dioxathiane 2-oxide；(4R,6R)-4,6-dimethyl-1,3,2-dioxathiane 2-oxide
• CAS: 29882-38-0
• 化学式: C₅H₁₀O₃S
• 分子量: 150.199
• InChiKey: USNQMYYMYHSTGH-RFZPGFLSSA-N

物化性质

• 沸点：
  198.8±9.0 °C(Predicted)
• 密度：
  1.28±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  54.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4,6-dimethyltrimethylene (cis,trans) sulphite 在 ruthenium trichloride 、 sodium periodate 作用下， 以 水 、 乙腈 为溶剂， 反应 1.0h， 以96%的产率得到(4R,6R)-4,6-dimethyl-1,3,2-dioxathiane-2,2-dioxide
  参考文献：
  名称：

  Schmidt反应使双环[3.3.0]辛烷-3,7-二酮不对称化：容易合成tecomanine

  摘要：

  顺式-双环[3.3.0]辛烷-3,7-二酮1的C 2v对称性通过选择性施密特反应改变，得到了3-氮杂双环[4.3.0] noanmine结构单元3b，可在短时间内使用（±）-tecomanine的合成4。上AsymmetricSchmidt反应1，采用（2S，4R）-2-叠氮基-4- hydroxypentane 14作为手性诱导剂，显示出令人鼓舞的对映亚甲基立体声分化的水平。

  DOI：

  10.1016/s0957-4166(97)00308-x
• 作为产物：
  描述：

  乙酰丙酮 生成 4,6-dimethyltrimethylene (cis,trans) sulphite
  参考文献：
  名称：

  Conformational analysis. XVIII. 1,3-Dithianes. Conformational preferences of alkyl substituents and the chair-boat energy difference

  摘要：

  DOI：

  10.1021/ja01038a050

文献信息

• Application of a lanthanide shift reagent in 17O n.m.r. spectroscopy to determine the stereochemical course of oxidation of cyclic sulphite diesters to cyclic sulphate diesters with ruthenium tetroxide
  作者：Gordon Lowe、Salvatore J. Salamone

  DOI：10.1039/c39830001392

  日期：——

  Cyclic sulphite diesters are rapidly oxidized to cyclic sulphate diesters with ruthenium tetroside in good yield; diastereotopically labelled cyclic [17O] sulphate diesters obtained by oxidation of diastereoisomeric cyclic sulphite diesters with ruthenium [17O] tetroxide are shown, by the effect of a lanthanide shift reagent on their 17O n.m.r. signals, to be formed with retention of configuration

  环式亚硫酸二酯与四溴化钌可快速氧化为环式硫酸二酯，收率良好。通过镧系元素转移试剂对其17 O nmr信号的影响，显示了通过用钌[ 17 O]四氧化物氧化非对映异构环状亚硫酸二酯而得到的非对位标记的环状[ 17 O]硫酸二酯。硫。
• Synthesis of sulfated mono- and ditertiary phosphines, complex chemistry and catalysis
  作者：H Gulyás、A Dobó、J Bakos

  DOI：10.1139/v01-040

  日期：2001.5.1

  have been prepared from commonly available alcohols. Nucleophilic cleavage of the cyclic sulfates affords a new type of water-soluble mono- and ditertiary phophines bearing -OSO3Li groups in distinguished positions in the molecular framework. Both phosphines have amphiphilic character. Reactions of the chiral 2 and the dppp analogue 5 with [Rh(COD)Cl]2 and Pt(PhCN)2Cl2 provide novel zwitterionic complexes

  环状和双环硫酸盐已由常用醇制备。环硫酸盐的亲核裂解提供了一种新型的水溶性单和二叔膦，在分子框架的不同位置带有 -OSO3Li 基团。两种膦都具有两亲性。手性 2 和 dppp 类似物 5 与 [Rh(COD)Cl]2 和 Pt(PhCN)2Cl2 的反应提供了新的两性离子配合物。2 和 5 的铑配合物已成功应用于苯乙烯和辛烯-1 的液体双相加氢甲酰化。当5的铑配合物用作苯乙烯加氢甲酰化的催化剂时，有机相中可以检测到小于4ppm的铑。关键词：环状硫酸盐，水溶性膦，两亲性，Rh配合物，Pt配合物，加氢甲酰化。
• A new route to achiral and chiral 1,2-bis(phosphino)ethanes, 1-arsino-2-phosphinoethanes, and 1,3-bis(phosphino)propanes and the molecular structure and catalytic activity of some rhodium(i) complexes derived thereof Dedicated to Professor Wolfdieter A. Schenk, a respected colleague and creative scientist, on the occasion of his 60th birthday.
  作者：Guido Fries、Justin Wolf、Kerstin Ilg、Bernhard Walfort、Dietmar Stalke、Helmut Werner

  DOI：10.1039/b401585a

  日期：——

  A series of unsymmetrical 1,2-bis(phosphino)ethanes R2PCH2CH2PR′2 (2a–d) and 1-arsino-2-phosphinoethanes R2AsCH2CH2PR′2 (3a–c) mainly with bulky substituents R and R′ were prepared from the cyclic sulfate 1 by stepwise cleavage of the carbon–oxygen bonds by LiPR2 and LiPR′2 or LiAsR2 and LiPR′2, respectively. Analogously, racemic mixtures of R2PCH2CH(Me)PPh2 (R = iPr 5a, Cy 5b) as well as the enantiomers (R)-5a, (R)-5b and (R)-tBu2PCH2CH(Me)PPh2 (R)-5c were obtained from the corresponding unsymmetrical cyclic sulfates 4 and (S)-4. On a similar route, the racemates of the 1,3-bis(phosphino)propanes R2PCH2CH2CH(Me)PPh2 (R = iPr 7, tBu 8), optically pure (R)-8 and (S,S)-iPr2PCH(Me)CH2CH(Me)PPh2 (S,S)-10 were prepared. The reaction of [RhCl(η4-C8H12)}2] with chelating ligands L–L, where L–L is R2PCH2P(men)2 (R = iPr, Ph; men = (1S,2R,5S)-menthyl), Cy2AsCH2P(men)2, or (R)-5a, (R)-5b, (R)-5c, (R)-8 and (S,S)-10, in the presence of AgPF6, gave the complexes [Rh(η4-C8H12)(L–L)]PF6 (12a–h) which were used as pre-catalysts in the hydrogenation of the methyl ester of α-acetamidocinnamic acid (ACM). Depending on L–L, the solvent, the temperature and the pressure of H2, optical yields of up to 69% ee were achieved. For two of the rhodium complexes, 12c and 12d, the molecular structures were determined by X-ray crystallography.

  一系列不对称的 1、通过 LiPR2 和 LiPR′2 或 LiAsR2 和 LiPR′2逐步裂解碳氧键，从环状硫酸盐 1 制备出了主要带有大取代基 R 和 R′的 1、2-双（膦）乙烷 R2PCH2C R′2 (2a-d)和 1-胂-2-膦乙烷 R2AsCH2C R′2 (3a-c)。同样，从相应的不对称环状硫酸盐 4 和 (S)-4 中得到了 R2PCH2CH(Me)PPh2 的外消旋混合物（R = iPr 5a、Cy 5b）以及对映体 (R)-5a、(R)-5b 和 (R)-tBu2PCH2CH(Me)PPh2 (R)-5c。按照类似的路线，制备了 1,3-双（膦）丙烷 R2PCH2CH2CH(Me)PPh2（R = iPr 7，tBu 8）的外消旋体、光学纯 (R)-8 和 (S,S)-iPr2PCH(Me)CH2CH(Me)PPh2 (S,S)-10。[RhCl(η4-C8H12)}2]与螯合配体 L-L 反应，其中 L-L 是 R2PCH2P(men)2 （R = iPr，Ph；men=(1S,2R,5S)-menthyl)、Cy2AsC (men)2 或 (R)-5a、(R)-5b、(R)-5c、(R)-8 和 (S,S)-10、得到了[Rh(η4- )(L-L)]PF6（12a-h）复合物，这些复合物被用作 α-乙酰胺肉桂酸（ACM）甲酯氢化反应的前催化剂。根据 L-L、溶剂、温度和 H2 压力的不同，光学产率可达 69% ee。通过 X 射线晶体学，确定了 12c 和 12d 这两种铑络合物的分子结构。
• Cazaux,L.; Maroni,P., Bulletin de la Societe Chimique de France, 1972, p. 773 - 779
  作者：Cazaux,L.、Maroni,P.

  DOI：——

  日期：——
• A general route to enantiomerically pure sulfoxides from a chiral sulfite
  作者：F. Rebiere、O. Samuel、L. Ricard、H. B. Kagan

  DOI：10.1021/jo00021a008

  日期：1991.10

  Enantiomerically pure cyclic chiral sulfite (S)-7 (trans stereochemistry) has been easily obtained in two steps from (S)-ethyl lactate. This compound was found to react cleanly with many organometallics to give crystalline sulfinates with high regioselectivity (> 90:10). Addition of a second organometallic transforms the purified sulfinate in excellent yield into a chiral sulfoxide (100% ee) of predictable absolute configuration. The mechanism and scope of this approach are discussed. This method completes the various other methods of preparation of chiral sulfoxides and is especially convenient for the preparation of tert-butyl sulfoxides. Examples for the synthesis of many chiral tert-butyl sulfoxides are given. The case of chiral sulfites derived from a C2 diol or of a chiral monoalcohol is also proposed as a route to chiral sulfinates, and some promising preliminary results have been obtained. The general main routes to obtain chiral sulfoxides from sulfites are also discussed.