(R)-dufulin | 1135520-85-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并噻唑类
• 英文名称: (R)-dufulin
• 英文别名: N-[(R)-[diethoxy(oxido)phosphaniumyl]-(2-fluorophenyl)methyl]-4-methyl-1,3-benzothiazol-2-amine
• CAS: 1135520-85-2
• 化学式: C₁₉H₂₂FN₂O₃PS
• 分子量: 408.433
• InChiKey: CLASFMUIFVKHQI-GOSISDBHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  94.7
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  dufulin 在 Daicel Chiralpak IA column 作用下， 以 乙醇 、 正己烷 为溶剂， 生成 (S)-dufulin 、 (R)-dufulin
  参考文献：
  名称：

  Enantioselective Degradation of Dufulin in Four Types of Soil

  摘要：

  In this study, enantioselective degradation of dufulin in four types of soil (Guiyang silty loam, Nanning silty clay, Hefei silty clay, and Harbin silty clay) was investigated under sterile and nonsterile conditions. Pesticide residues in soil samples were extracted with acetonitrile. S-(+)-Dufulin and R-(-)-dufulin were separated and determined on an amylose tris(3,5-dimethylphenylcarbamate) (Chiralpak IA) chiral column by normal phase high-performance liquid chromatography (HPLC). The absolute configurations of dufulin enantiomers were determined by obtaining experimental and computed circular dichroism spectra. Dufulin enantiomers were found to be configurationally stable in the selected soils, and no interconversion was observed during the incubation of enantiopure S-(+)- or R-(-)-dufulin under nonsterile conditions. Compared to the half-life (t(1/2)) of dufulin in sterile soils, the degradation rate was higher in nonsterile soils, which suggests that dufulin degradation can be attributed primarily to microbial activity in soils used for agricultural cultivation. Furthermore, enantiopure S-(+)-dufulin degraded more rapidly than its antipode. This suggests that use of enantiopure S-(+)-dufulin could exert less disturbance to soil bioactivity and contribute less to environmental pollution.

  DOI：

  10.1021/jf404130d

文献信息

• Asymmetric Synthesis of α-Aminophosphonates Using the Inexpensive Chiral Catalyst 1,1’-Binaphthol Phosphate
  作者：Weiming Xu、Sha Zhang、Song Yang、Lin-Hong Jin、Pinaki S. Bhadury、De-Yu Hu、Yuping Zhang

  DOI：10.3390/molecules15085782

  日期：——

  Asymmetric addition under mild conditions of dialkyl phosphites on aldimines derived from cinnamaldehyde catalyzed by the inexpensive chiral organocatalyst (R)-3,3’-[4-fluorophenyl]2-1,1’-binaphthol phosphate has been found effective to give new α-amino-phosphonates 9 in moderate yields (30–65%) and enantiomeric excess (8.4%–61.9%).

  在温和条件下，廉价的手性有机催化剂(R)-3,3'-[4-氟苯基]2-1,1'-联萘酚磷酸酯催化肉桂醛衍生的醛亚胺与二烷基亚磷酸酯的不对称加成反应，已被发现是有效的，能够以中等产率(30-65%)和立体选择性(8.4%-61.9%)得到新的α-氨基亚磷酸酯9。
• Origins of enantioselectivity in the chiral Brønsted acid catalyzed hydrophosphonylation of imines
  作者：Fu-Qiang Shi、Bao-An Song

  DOI：10.1039/b815008g

  日期：——

  computational investigation of the mechanism and the origins of enantioselectivity in the asymmetric synthesis of α-amino phosphonates by an enantioselective hydrophosphonylation of imines catalyzed by chiral Brønsted acids are reported. It was found that the enantioselectivity observed in the enantioselective hydrophosphonylation of the imine with a benzothiazole moiety was poor. A detailed computational

  基于实验和基于ONIOM的α不对称合成中对映选择性的机理和起源的计算研究结果据报道，通过手性布朗斯台德酸催化的亚胺的对映选择性氢膦酰化生成α-氨基膦酸酯。发现在具有苯并噻唑部分的亚胺的对映选择性氢膦酰基化中观察到的对映选择性差。用两层ONIOM（B3LYP / 6–31G（d）/ AM1）方法对所研究反应的机理进行了详细的计算研究，以探索对映选择性的起源。计算表明，所研究的反应是一个两步过程，涉及质子转移和亲核加成，这是立体控制步骤。研究的反应比单配位途径更喜欢双配位途径。对三种催化剂和两种亲核试剂表现出的不同对映选择性进行了合理化。si腐蚀的能量要比re腐蚀的能量高，仅为0.1 kcal / mol，这很好地解释了在具有苯并噻唑部分的亚胺的对映选择性氢膦酰化反应中观察到的低ee值。手性布朗斯台德酸催化的膦酸酯-亚磷酸酯互变异构的能垒甲苯 仅为1.8 kcal / mol，这可以解释为什么所研究的反应可以在室温下发生。