(R,R)-1-benzyl-3,4-bis(isopropylsulfanyl)pyrrolidine | 219505-58-5

• 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: (R,R)-1-benzyl-3,4-bis(isopropylsulfanyl)pyrrolidine
• 英文别名: (-)-1-benzyl-3,4-bis(isopropylsulfanyl)pyrrolidine；(3R,4R)-1-Benzyl-3,4-bis[(propan-2-yl)sulfanyl]pyrrolidine；(3R,4R)-1-benzyl-3,4-bis(propan-2-ylsulfanyl)pyrrolidine
• CAS: 219505-58-5
• 化学式: C₁₇H₂₇NS₂
• 分子量: 309.54
• InChiKey: QLMCXIZFBOMTOJ-IAGOWNOFSA-N

物化性质

• 沸点：
  410.4±45.0 °C(Predicted)
• 密度：
  1.07±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  53.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  bis(cyclooctadiene)rhodium(I) perchlorate 、 (R,R)-1-benzyl-3,4-bis(isopropylsulfanyl)pyrrolidine 以 二氯甲烷 为溶剂， 以76%的产率得到[Rh(1,5-cyclooctadiene)((R,R)-1-benzyl-3,4-bis(isopropylsulfanyl)pyrrolidine)]ClO4 * 1/2 CH2Cl2
  参考文献：
  名称：

  Synthesis, reactivity and catalytic properties of rhodium complexes of (R,R)-1-benzyl-3,4-dithioetherpyrrolidines

  摘要：

  Complexes [Rh(cod)(degusR)]ClO4, where cod is 1,5-cyclooctadiene and degusR represents the homochiral dithioethers (R,R)-1-benzyl-3,4-bis(methylsulfanyl)pyrrolidine, (R,R)-1-benzyl-3,4-bis(isopropylsulfanyl)pyrrolidine and (R,R)-1-benzyl-3,4-bis(phenylsulfanyl)pyrrolidine were prepared and characterized. Their reactivity with CO and PPh3 was investigated. The complexes were assayed as catalysts in hydroformylation of styrene, hydrogenation of acrylic acids and hydroboration of styrene. Although these complexes containing dithioethers behave as catalytic precursors in hydroformylation reaction, the results suggest that mononuclear hydride rhodium carbonyl species is responsible for the catalytic activity. The cationic complexes are not active in the hydrogenation of acrylic acids in the conditions tested. These complexes are moderately active in the hydroboration of styrene with catecholborane, but their selectivities are not satisfactory. (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0020-1693(99)00309-6
• 作为产物：
  描述：

  (3S,4S)-1-苄基吡咯烷-3,4-二醇 在 吡啶 、 sodium hydride 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 1.17h， 生成 (R,R)-1-benzyl-3,4-bis(isopropylsulfanyl)pyrrolidine
  参考文献：
  名称：

  铱与含有刚性环状骨架的新的1,2-二硫醚手性配体形成配合物。在均相催化不对称加氢中的应用†

  摘要：

  新的手性二硫醚化合物（ - ） - 1-苄基-3,4-双（甲基硫基）吡咯烷（ - ） - degusme，（ - ） - 1-苄基-3,4-二（异丙硫基）吡咯烷（ - ） - deguspr我由（+）- L-酒石酸制备和（+）-1-苄基-3,4-双（苯硫烷基）吡咯烷（+）-去氟。将二硫醚化合物添加到[Ir（cod）2 ] BF 4的二氯甲烷溶液中，得到手性阳离子络合物[Ir（cod）{（–）-degusme}] BF 4 1 [Ir（cod）{（–） -deguspr我}] BF 4 ·CH 2氯2 2和物[Ir（COD）{（+） - degusph}] BF 4 3.二硫醚配体由置换PPH 3在配合物1、2和3中提供[Ir（cod）（PPh 3）2 ] BF 4配合物。在–70°C下向1、2和3添加H 2得到顺二氢化铱（III）复合物[IrH 2（cod）L] BF 4 [L =（-）-degusme

  DOI：

  10.1039/a803626h

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。
• Iridium complexes with new 1,2-dithioether chiral ligands containing a rigid cyclic backbone. Application in homogeneous catalytic asymmetric hydrogenation †
  作者：Montserrat Diéguez、Aurora Ruiz、Carmen Claver、Maria M. Pereira、António M. d’A. Rocha Gonsalves

  DOI：10.1039/a803626h

  日期：——

  dichloromethane solution of [Ir(cod)2]BF4 afforded the chiral cationic complexes [Ir(cod)(–)-degusme}]BF4 1 [Ir(cod)(–)-deguspri}]BF4·CH2Cl2 2 and [Ir(cod)(+)-degusph}]BF4 3. The dithioether ligands were replaced by PPh3 in complexes 1, 2 and 3 providing the [Ir(cod)(PPh3)2]BF4 complex. The addition of H2 to 1, 2 and 3 at –70 °C gave cis-dihydridoiridium(III) complexes [IrH2(cod)L]BF4 [L = (–)-degusme 4,

  新的手性二硫醚化合物（ - ） - 1-苄基-3,4-双（甲基硫基）吡咯烷（ - ） - degusme，（ - ） - 1-苄基-3,4-二（异丙硫基）吡咯烷（ - ） - deguspr我由（+）- L-酒石酸制备和（+）-1-苄基-3,4-双（苯硫烷基）吡咯烷（+）-去氟。将二硫醚化合物添加到[Ir（cod）2 ] BF 4的二氯甲烷溶液中，得到手性阳离子络合物[Ir（cod）（–）-degusme}] BF 4 1 [Ir（cod）（–） -deguspr我}] BF 4 ·CH 2氯2 2和物[Ir（COD）（+） - degusph}] BF 4 3.二硫醚配体由置换PPH 3在配合物1、2和3中提供[Ir（cod）（PPh 3）2 ] BF 4配合物。在–70°C下向1、2和3添加H 2得到顺二氢化铱（III）复合物[IrH 2（cod）L] BF 4 [L =（-）-degusme
• Synthesis, reactivity and catalytic properties of rhodium complexes of (R,R)-1-benzyl-3,4-dithioetherpyrrolidines
  作者：M Diéguez、A Ruiz、C Claver、M.M Pereira、M.T Flor、J.C Bayón、M.E.S Serra、A.M.d’A Rocha Gonsalves

  DOI：10.1016/s0020-1693(99)00309-6

  日期：1999.11

  Complexes [Rh(cod)(degusR)]ClO4, where cod is 1,5-cyclooctadiene and degusR represents the homochiral dithioethers (R,R)-1-benzyl-3,4-bis(methylsulfanyl)pyrrolidine, (R,R)-1-benzyl-3,4-bis(isopropylsulfanyl)pyrrolidine and (R,R)-1-benzyl-3,4-bis(phenylsulfanyl)pyrrolidine were prepared and characterized. Their reactivity with CO and PPh3 was investigated. The complexes were assayed as catalysts in hydroformylation of styrene, hydrogenation of acrylic acids and hydroboration of styrene. Although these complexes containing dithioethers behave as catalytic precursors in hydroformylation reaction, the results suggest that mononuclear hydride rhodium carbonyl species is responsible for the catalytic activity. The cationic complexes are not active in the hydrogenation of acrylic acids in the conditions tested. These complexes are moderately active in the hydroboration of styrene with catecholborane, but their selectivities are not satisfactory. (C) 1999 Elsevier Science S.A. All rights reserved.