di(2-thienyl)germane | 182997-62-2

• 分子结构分类: 有机化合物 - 有机金属化合物 - 金属芳基
• 英文名称: di(2-thienyl)germane
• 英文别名: bis(2-thienyl)germane；Dithiophen-2-ylgermane；dithiophen-2-ylgermane
• CAS: 182997-62-2
• 化学式: C₈H₈GeS₂
• 分子量: 240.874
• InChiKey: SAZATBRSMBXNIO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.93
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  56.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-甲基二乙醇胺 、 di(2-thienyl)germane 以 neat (no solvent) 为溶剂， 以81%的产率得到2,2-di(2-thienyl)-6-methyl-1,3-dioxa-6-aza-2-germacyclooctane
  参考文献：
  名称：

  A new pathway for the synthesis of 1,3-dioxa-6-aza-2-germacyclooctanes: molecular structure of 2,2-di(2-thienyl)-6-methyl-1,3-dioxa-6-aza-2-germacyclooctane

  摘要：

  A novel reaction pathway has been applied for the synthesis of 1,3-dioxa-6-aza-2-germacyclooctanes. Compounds of this type were obtained by the dehydrocondensation of di(2-thienyl)germane and diethanolamines without a catalyst. The molecular structure of 2,2-di(2-thienyl)-6-methyl-1,3-dioxa-5-azacyclooctane has been determined by X-ray diffraction study. The interatomic N --> Ge distance of 2.446 Angstrom indicates the presence of a weak transannular bond.

  DOI：

  10.1016/0022-328x(96)06374-7
• 作为产物：
  描述：

  2-溴噻吩 、 germanium(II) bromide 在 n-butyl lithium 作用下， 以 乙醚 、 正己烷 为溶剂， 以64%的产率得到di(2-thienyl)germane
  参考文献：
  名称：

  Trihydrogermyl-substituted thiophenes

  摘要：

  将2-溴或2,5-二溴噻吩在低温下与等量的正丁基锂反应，然后加入溴基锗，分别获得2-锗基-2和2,5-二(锗基)-噻吩，产率为44%和82%。2-溴噻吩与四乙氧基锗和镁的原位格氏反应仅得到了低产率的2-[三(乙氧基)锗基]噻吩。尝试使用LiAlH4将该产物转化为三氢化物，仅得到微量的2。二(2-噻吩基)锗可通过2-锂噻吩与二溴锗反应获得（摩尔比2:1，产率64%）。产品已通过分析和光谱方法进行表征。73Ge NMR光谱显示只有宽共振，没有可辨别的73Ge–1H耦合，这是由于取代基的低对称性。2和3的分子几何结构已使用标准的从头算量子化学方法计算，结果与最近报告的类似硅噻吩的结果相似。没有证据表明存在显著的分子内Ge⋯S相互作用。

  DOI：

  10.1039/b004024j

文献信息

• Cu-Catalyzed Enantioselective Hydrogermylation: Asymmetric Synthesis of Unnatural β-Germyl α-Amino Acids
  作者：Weidong Lin、Lijun You、Wei Yuan、Chuan He

  DOI：10.1021/acscatal.2c04571

  日期：2022.12.2

  A copper-catalyzed asymmetric synthesis of unnatural β-germyl α-amino acids is developed. This process undergoes an intermolecular enantioselective hydrogermylation of dehydroalanines with dihydrogermanes and trihydrogermanes, giving access to a variety of chiral β-germyl α-amino acid derivatives in decent yields with good to excellent enantioselectivities. Mechanistic studies indicate that a [Cu–Ge]

  开发了非天然 β-甲锗烷基 α-氨基酸的铜催化不对称合成。该过程经历了脱氢丙氨酸与二氢锗烷和三氢锗烷的分子间对映选择性氢化锗化作用，从而以良好的收率获得各种手性 β-甲锗烷基 α-氨基酸衍生物，并具有良好的对映选择性。机理研究表明，[Cu-Ge] 物种是该氢化锗化过程中的关键中间体，而不是通常在铜催化的氢化硅烷化反应中产生的 [Cu-H] 物种。受保护的 β-甲锗烷基 α-氨基酸的进一步立体特异性转化产生了许多对映体富集的含锗功能分子，这些分子可能在许多领域都有用。
• A new pathway for the synthesis of 1,3-dioxa-6-aza-2-germacyclooctanes: molecular structure of 2,2-di(2-thienyl)-6-methyl-1,3-dioxa-6-aza-2-germacyclooctane
  作者：Edmunds Lukevics、Sergey Belyakov、Olga Pudova

  DOI：10.1016/0022-328x(96)06374-7

  日期：1996.10

  A novel reaction pathway has been applied for the synthesis of 1,3-dioxa-6-aza-2-germacyclooctanes. Compounds of this type were obtained by the dehydrocondensation of di(2-thienyl)germane and diethanolamines without a catalyst. The molecular structure of 2,2-di(2-thienyl)-6-methyl-1,3-dioxa-5-azacyclooctane has been determined by X-ray diffraction study. The interatomic N --> Ge distance of 2.446 Angstrom indicates the presence of a weak transannular bond.
• Trihydrogermyl-substituted thiophenes
  作者：Frank Riedmiller、Hubert Schmidbaur

  DOI：10.1039/b004024j

  日期：——

  Treatment of 2-bromo- or 2,5-dibromo-thiophene with equivalent quantities of n-butyllithium at low temperature, followed by bromogermane, afforded 2-germyl- 2 and 2,5-di(germyl)-thiophene 3 in 44 and 82% yields, respectively. The in situ Grignard reaction of 2-bromothiophene with tetra(ethoxy)germane and magnesium gave low yields of 2-[tri(ethoxy)germyl]thiophene 1. Attempts to convert this product into the trihydride using LiAlH4 yielded only traces of 2. Bis(2-thienyl)germane 4 is available from 2-lithiothiophene and dibromogermane (molar ratio 2∶1, 64% yield). The products have been characterized by analytical and spectroscopic methods. The 73Ge NMR spectra show only broad resonances without discernible 73Ge–1H coupling owing to the low symmetry of the substituents. The molecular geometries of 2 and 3 have been calculated using standard ab initio quantum chemical methods. The results are similar to those for analogous silylthiophenes reported recently. There is no evidence for significant intramolecular Ge⋯S interactions.

  将2-溴或2,5-二溴噻吩在低温下与等量的正丁基锂反应，然后加入溴基锗，分别获得2-锗基-2和2,5-二(锗基)-噻吩，产率为44%和82%。2-溴噻吩与四乙氧基锗和镁的原位格氏反应仅得到了低产率的2-[三(乙氧基)锗基]噻吩。尝试使用LiAlH4将该产物转化为三氢化物，仅得到微量的2。二(2-噻吩基)锗可通过2-锂噻吩与二溴锗反应获得（摩尔比2:1，产率64%）。产品已通过分析和光谱方法进行表征。73Ge NMR光谱显示只有宽共振，没有可辨别的73Ge–1H耦合，这是由于取代基的低对称性。2和3的分子几何结构已使用标准的从头算量子化学方法计算，结果与最近报告的类似硅噻吩的结果相似。没有证据表明存在显著的分子内Ge⋯S相互作用。