(pR,pR,S_S,S_S)-2,2″-bis(p-tolylsulfinyl)-1,1″-biferrocene | 358721-80-9

• 英文名称: (pR,pR,S_S,S_S)-2,2″-bis(p-tolylsulfinyl)-1,1″-biferrocene
• 英文别名: (S,S,S(p),S(p))-2,2''-bis[(4-methylphenyl)sulfinyl]-1,1''-ferrocene
• CAS: 358721-80-9
• 化学式: C₃₄H₃₀Fe₂O₂S₂
• 分子量: 646.437
• InChiKey: ALYOREPPZNUWPX-XVTMMIJWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (pR,pR,S_S,S_S)-2,2″-bis(p-tolylsulfinyl)-1,1″-biferrocene 在 叔丁基锂 、 三甲基氯化锡 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.08h， 以43%的产率得到(pS,pR,S_S)-2-(trimethylstannyl)-2″-(p-tolylsulfinyl)-1,1″-biferrocene
  参考文献：
  名称：

  Redox-Switchable Chiral Anions and Cations Based on Heteroatom-Fused Biferrocenes

  摘要：

  A new class of planar chiral heteroatom-bridged biferrocene species was prepared using (pR,pR,S-s,S-s)-2,2 ''-bis(p-tolylsulfinyl)-1,1 ''-biferrocene (pR,pR,S-s,S-s)-2 as a readily accessible precursor. Initially, one of the sulfinate groups in compound 2 is replaced with a trimethylstannyl or dimesitylboryl group. Replacement of the second sulfinate group with t-BuLi then results in cyclization to give the Me2Sn-bridged species (pS,pS)-4Sn and the Mes(2)B-bridged borate anion [(pS,pS)-4B](-). The products are redox active, as cyclic and square wave voltammetry data of (pS,pS)-4Sn and [Li(12-c-4)(2)] [(pS,pS)-4B] reveal two separate reversible oxidation events. events. The mixed-valent species [(pS,pS)-4Sn](+) and (pS,pS)-4B can also be obtained by chemical oxidation with AgPF6 or by simple exposure to air, respectively. A comparison of X-ray crystal structures reveals that the oxidized (mixed-valent) species contain distinct Fe(:1) and Fe(III) sites, but UV visible NIR spectra display IVCT bands at ca. 4000 and 5000 cm(-1), indicative of electronic coupling in solution. All compounds are obtained in enantiomerically pure form, suggesting potential use as switchable chiral anions and cations.

  DOI：

  10.1021/acs.organomet.5b00577
• 作为产物：
  描述：

  (S)-ferrocenyl p-tolyl sulfoxide 在 lithium diisopropyl amide 、 zinc dibromide 、 bis(acetylacetonate)nickel(II) 、 2-氯-2-苯基苯乙酮 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以60%的产率得到(pR,pR,S_S,S_S)-2,2″-bis(p-tolylsulfinyl)-1,1″-biferrocene
  参考文献：
  名称：

  Redox-Switchable Chiral Anions and Cations Based on Heteroatom-Fused Biferrocenes

  摘要：

  A new class of planar chiral heteroatom-bridged biferrocene species was prepared using (pR,pR,S-s,S-s)-2,2 ''-bis(p-tolylsulfinyl)-1,1 ''-biferrocene (pR,pR,S-s,S-s)-2 as a readily accessible precursor. Initially, one of the sulfinate groups in compound 2 is replaced with a trimethylstannyl or dimesitylboryl group. Replacement of the second sulfinate group with t-BuLi then results in cyclization to give the Me2Sn-bridged species (pS,pS)-4Sn and the Mes(2)B-bridged borate anion [(pS,pS)-4B](-). The products are redox active, as cyclic and square wave voltammetry data of (pS,pS)-4Sn and [Li(12-c-4)(2)] [(pS,pS)-4B] reveal two separate reversible oxidation events. events. The mixed-valent species [(pS,pS)-4Sn](+) and (pS,pS)-4B can also be obtained by chemical oxidation with AgPF6 or by simple exposure to air, respectively. A comparison of X-ray crystal structures reveals that the oxidized (mixed-valent) species contain distinct Fe(:1) and Fe(III) sites, but UV visible NIR spectra display IVCT bands at ca. 4000 and 5000 cm(-1), indicative of electronic coupling in solution. All compounds are obtained in enantiomerically pure form, suggesting potential use as switchable chiral anions and cations.

  DOI：

  10.1021/acs.organomet.5b00577

文献信息

• Synthesis, coordination behaviour, structural features and use in asymmetric hydrogenations of bifep-type biferrocenes
  作者：Gustavo Espino、Li Xiao、Michael Puchberger、Kurt Mereiter、Felix Spindler、Blanca R. Manzano、Félix A. Jalón、Walter Weissensteiner

  DOI：10.1039/b816544k

  日期：——

  A protocol for the synthesis of C2- and C1-symmetric 2,2″-diarylphosphino-substituted biferrocenes (bifep-type ligands) is presented and the preparation of four representatives is described [(Sp,Sp)-2-R12P-2″- R22P-1,1″-biferrocene; 1 (bifep): R1 = R2 = Ph; 2: R1 = Ph, R2 = Cy; 3: R1 = R2 = 3,5-Me2C6H3; 4: R1 = 3,5-Me2−4-OMe-C6H2, R2 = 3,5-(CF3)2C6H3]. In addition, the synthesis of three palladium(II) complexes ([PdX2(L)], 10: L = 1, X = Cl; 11: L = 4, X = Cl; 12: L = 1, X = C6F5 and of four bifep ruthenium complexes (13: [RuCl(p-cymene)(1)]PF6; 14: [RuI(p-cymene)(1)]PF6; 15: [RuCl(benzene)(1)]PF6; 16: [RuI(p-cymene)(1)]I) is reported. In the solid state the biferrocene unit of complexes 10, 11 and 15 adopt either a (P)-shaped (10) or an (M)-shaped (11, 15) conformation. In solution, palladium complexes 10 and 11 are present as equilibrium mixtures of rapidly interconverting (P)- and (M)-shaped conformers. Rhodium- and iridium-mediated asymmetric hydrogenations of a number of olefins and one imine give products with only low to moderate enantiomeric excess, while in the ruthenium-catalyzed hydrogenation of ketones a maximum e.e. of 82% is obtained. The low enantioselectivities are assumed to be related to the conformational flexibility of bifep-type ligands.

  本文介绍了一种合成 C2- 和 C1-对称 2,2″-二芳基膦取代的双铁金属化合物（bifep型配体）的协议，并描述了四种代表性化合物的制备 [(Sp,Sp)-2-R12P-2″- R22P-1,1″-双铁金属化合物；1 (bifep): R1 = R2 = Ph; 2: R1 = Ph, R2 = Cy; 3: R1 = R2 = 3,5-Me2C6H3; 4: R1 = 3,5-Me2−4-OMe-C6H2, R2 = 3,5-(CF3)2C6H3]。此外，还报道了三种钯(II)配合物的合成（[PdX2(L)], 10: L = 1, X = Cl; 11: L = 4, X = Cl; 12: L = 1, X = C6F5）以及四种 bifep 钌配合物的合成（13: [RuCl(p-cymene)(1)]PF6; 14: [RuI(p-cymene)(1)]PF6; 15: [RuCl(benzene)(1)]PF6; 16: [RuI(p-cymene)(1)]I）。在固态下，配合物 10、11 和 15 的双铁金属单元采取 (P)-形（10）或 (M)-形（11、15）构象。在溶液中，钯配合物 10 和 11 以快速相互转换的 (P)- 和 (M)-形构象的平衡混合物存在。铑和铱催化的不对称氢化反应对多种烯烃和一种亚胺的产物具有较低至中等的光学纯度，而在钌催化的酮氢化反应中，最高 e.e. 为 82%。低选择性被认为是由于 bifep 型配体的构象灵活性所致。