(-)-2,2-dimethyl-4,5-bis(methylsulfanylmethyl)-1,3-dioxolane | 65591-58-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (-)-2,2-dimethyl-4,5-bis(methylsulfanylmethyl)-1,3-dioxolane
• 英文别名: (-)-2,3-isopropylidene-1,4-dimethylthioether-L-threitol；(4R,5R)-2,2-Dimethyl-4,5-bis[(methylsulfanyl)methyl]-1,3-dioxolane；(4R,5R)-2,2-dimethyl-4,5-bis(methylsulfanylmethyl)-1,3-dioxolane
• CAS: 65591-58-4
• 化学式: C₉H₁₈O₂S₂
• 分子量: 222.373
• InChiKey: SWUOZPXVLJNEBP-YUMQZZPRSA-N

物化性质

• 沸点：
  295.2±15.0 °C(Predicted)
• 密度：
  1.047±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  69.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  bis(cyclooctadiene)rhodium(I) perchlorate 、 (-)-2,2-dimethyl-4,5-bis(methylsulfanylmethyl)-1,3-dioxolane 以 二氯甲烷 为溶剂， 以97%的产率得到[Rh(1,5-cyclooctadiene)((-)-2,3-isopropylidene-1,4-dimethylthioether-L-threitol)]ClO4 * 1/2 CH2Cl2
  参考文献：
  名称：

  Rhodium cationic complexes using dithioethers as chiral ligands. Application in styrene hydroformylation

  摘要：

  Addition of the dithioethers (-)-DIOSR2 (R = Me, Pr-i) (2,3-O-isopropylidene-1,4-dimethyl (and diisopropyl) thioether-L-threitol) to a dichloromethane solution of [Rh(COD)(2)]ClO4, (COD = 1,5-cyclooctadiene) yielded the mononuclear complexes [Rh(COD)(DIOSR2)]ClO4. X-ray diffraction methods showed that the [Rh(COD)((DIOSPr2)-Pr-i)]ClO4 complex had an square-planar coordination geometry at the rhodium atom with the Pr-i groups in anti position. Cyclooctadiene complexes react with carbon monoxide to form dinuclear tetracarbonylated complexes [(CO)(2)Rh(mu-DIOSR2)(2)(CO)(2)](ClO4)(2). [Rh(COD)(DIOSR2)]ClO4 are active catalyst precursors in styrene hydroformylation at 30 atm and 65 degrees C which give conversions of up to 99% with a regioselectivity in 2-phenylpropanal as high as 74%. In all cases enantioselectivities are low. (C) 1998 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(97)00692-x
• 作为产物：
  描述：

  (4S,5S)-2,2-二甲基-1,3-二氧戊环-4,5-二甲醇 在 吡啶 、 sodium hydride 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 0.92h， 生成 (-)-2,2-dimethyl-4,5-bis(methylsulfanylmethyl)-1,3-dioxolane
  参考文献：
  名称：

  环辛-1,5-二烯和手性二硫醚配体的阳离子铱（I）配合物的合成和反应性。在不对称氢化中用作催化剂前体†

  摘要：

  新的手性二硫醚化合物（–）-2,2-二甲基-4,5-双（异丙基硫烷基甲基）-1,3-二氧戊环（–）-二异丙醇和（+）-2,2-二甲基-4,5-双（由（+）- L-酒石酸二乙酯制备苯基硫烷基甲基）-1，3-二氧戊环（+）-二恶烷。设计了一种替代的合成方法，用于制备前述的双（甲基硫烷基甲基）二硫醚（-）-二恶英。通过将二硫醚与不同的（cycloocta-1,5-diene）铱（I）配位，手性阳离子络合物[Ir（cod）{（–）-diosme}] BF 4 1，[Ir（cod）{（ –）-diospr}] BF 4 ·CH 2 Cl 2 2和[Ir（cod）{（+）-diosph}] BF 4 3的合成，然后在1 H，13下进行研究13 C NMR和FAB质谱。配合物与CO反应，得到相应的双核四羰基[Ir 2（μ-L）2（CO）4 ] [BF] 2 4-6。二硫醚配体在1-3中被PPh 3取代，提供[Ir（cod）（PPh

  DOI：

  10.1039/a704611a

文献信息

• Synthesis and stereochemical study of new complexes of Pd and Pt with chiral dithioether ligands
  作者：Montserrat Diéguez、Aurora Ruiz、Anna Maria Masdeu-Bultó、Carmen Claver

  DOI：10.1039/b004403m

  日期：——

  New palladium(II) and platinum(II) complexes with two families of chiral dithioether ligands, (−)-1-benzyl-3,4-bis(methylsulfanyl)pyrrolidine (−)-degusMe2, (−)-1-benzyl-3,4-bis(isopropylsulfanyl)pyrrolidine (−)-degusPri2, (+)-1-benzyl-3,4-bis(phenylsulfanyl)pyrrolidine (+)-degusPh2, (−)-2,2-dimethyl-4,5-bis(methylsulfanylmethyl)-1,3-dioxolane (−)-diosMe2 and (−)-4,5-bis(isopropylsulfanylmethyl)-2,2-dimethyl-1,3-dioxolane (−)-diosPri2, have been prepared and characterised by NMR. The complexes [PdCl2(−)-degusMe2}], [PdCl2(+)-degusPh2}] and [PdCl2(−)-diosMe2}] show a mixture of two diastereomers in solution at room temperature. VT-NMR indicates that there is no interconversion between diastereomers at room temperature. Complex [Pt(cod)(−)-diosMe2}][BF4]2 is extremely fluxional and its diastereomers did not show isolated NMR resonances even at −90 °C. The complexes [PdCl2(−)-degusPri2}], [PdCl2(−)-diosPri2}] and [Pt(cod)(−)-diosPri2}][BF4]2, which contain a more hindered ligand, seem to be well suited for use in enantioselective catalysis because only one diastereomer is present.

  新的钯(II)和铂(II)配合物与两个系列的手性二硫醚配体，(-)-1-苄基-3,4-双(甲硫基)吡咯烷(-)-degusMe2，(-)-1-苄基-3,4-双(异丙基硫基)吡咯烷(-)-degusPri2，(+)-1-苄基-3、(+)-degusPh2、(-)-2,2-二甲基-4,5-双(甲基硫甲基)-1,3-二氧戊环(-)-diosMe2 和 (-)-4,5-双(异丙基硫甲基)-2,2-二甲基-1,3-二氧戊环(-)-diosPri2。室温下，[PdCl2(-)-degusMe2}]、[PdCl2(+)-degusPh2}]和[PdCl2(-)-diosMe2}]复合物在溶液中显示出两种非对映异构体的混合物。VT-NMR 显示，非对映异构体之间在室温下没有相互转化。[Pt(cod)(-)-diosMe2}][BF4]2 复合物具有极强的通性，其非对映异构体即使在 -90 ℃ 下也不会显示出独立的核磁共振共振。[PdCl2(-)-degusPri2}]、[PdCl2(-)-diosPri2}]和[Pt(cod)(-)-diosPri2}][BF4]2 复合物含有更多受阻配体，由于只存在一种非对映异构体，因此似乎非常适合用于对映选择催化。
• Synthesis and reactivity of cationic iridium(I) complexes of cycloocta-1,5-diene and chiral dithioether ligands. Application as catalyst precursors in asymmetric hydrogenation †
  作者：Montserrat Diéguez、Aránzazu Orejón、Anna M. Masdeu-Bultó、Raouf Echarri、Sergio Castillón、Carmen Claver、Aurora Ruiz

  DOI：10.1039/a704611a

  日期：——

  2-dimethyl-4,5-bis(isopropylsulfanylmethyl)-1,3-dioxolane (–)-diospr and (+)-2,2-dimethyl-4,5-bis(phenylsulfanylmethyl)-1,3-dioxolane (+)-diosph were prepared from diethyl (+)-L-tartrate. An alternative synthetic method for preparing the previously described bis(methylsulfanylmethyl) dithioether (–)-diosme was devised. By co-ordinating of the dithioethers to different (cycloocta-1,5-diene)iridium(I) compounds

  新的手性二硫醚化合物（–）-2,2-二甲基-4,5-双（异丙基硫烷基甲基）-1,3-二氧戊环（–）-二异丙醇和（+）-2,2-二甲基-4,5-双（由（+）- L-酒石酸二乙酯制备苯基硫烷基甲基）-1，3-二氧戊环（+）-二恶烷。设计了一种替代的合成方法，用于制备前述的双（甲基硫烷基甲基）二硫醚（-）-二恶英。通过将二硫醚与不同的（cycloocta-1,5-diene）铱（I）配位，手性阳离子络合物[Ir（cod）（–）-diosme}] BF 4 1，[Ir（cod）（ –）-diospr}] BF 4 ·CH 2 Cl 2 2和[Ir（cod）（+）-diosph}] BF 4 3的合成，然后在1 H，13下进行研究13 C NMR和FAB质谱。配合物与CO反应，得到相应的双核四羰基[Ir 2（μ-L）2（CO）4 ] [BF] 2 4-6。二硫醚配体在1-3中被PPh 3取代，提供[Ir（cod）（PPh
• Rhodium cationic complexes using dithioethers as chiral ligands. Application in styrene hydroformylation
  作者：A. Orejón、A.M. Masdeu-Bultó、R. Echarri、M. Diéguez、J. Forniés-Cámer、C. Claver、C.J. Cardin

  DOI：10.1016/s0022-328x(97)00692-x

  日期：1998.5

  Addition of the dithioethers (-)-DIOSR2 (R = Me, Pr-i) (2,3-O-isopropylidene-1,4-dimethyl (and diisopropyl) thioether-L-threitol) to a dichloromethane solution of [Rh(COD)(2)]ClO4, (COD = 1,5-cyclooctadiene) yielded the mononuclear complexes [Rh(COD)(DIOSR2)]ClO4. X-ray diffraction methods showed that the [Rh(COD)((DIOSPr2)-Pr-i)]ClO4 complex had an square-planar coordination geometry at the rhodium atom with the Pr-i groups in anti position. Cyclooctadiene complexes react with carbon monoxide to form dinuclear tetracarbonylated complexes [(CO)(2)Rh(mu-DIOSR2)(2)(CO)(2)](ClO4)(2). [Rh(COD)(DIOSR2)]ClO4 are active catalyst precursors in styrene hydroformylation at 30 atm and 65 degrees C which give conversions of up to 99% with a regioselectivity in 2-phenylpropanal as high as 74%. In all cases enantioselectivities are low. (C) 1998 Elsevier Science S.A. All rights reserved.