双语化学辞典Chem Lexicon
概念 · 立体化学 · 立体异构 Stereochemistry · Stereoisomerism

阻转异构Atropisomer

拼音Pinyin zǔ zhuǎn yì gòu 别名Also 阻转异构体; atropisomerism

定义Definition

阻转异构体是由于单键旋转受到严重空间位阻、能垒足够高而能够分离的构象异构体。最典型的是邻位有大取代基的联芳烃,它们具有轴手性。

Atropisomers are conformers separable because rotation about a single bond is so hindered that the barrier is high. The classic cases are biaryls with bulky ortho substituents, which possess axial chirality.

判据Criterion

大木道则(Ōki)给出的经验定义:室温下异构体半衰期至少 1000 秒(约 16.7 分钟),对应旋转能垒约 93 kJ/mol 以上。药物研发中常按能垒把阻转异构分为三类(< 84、84–117、> 117 kJ/mol)。

Ōki’s working definition: a half-life of at least 1000 s at room temperature, corresponding to a barrier above ~93 kJ/mol. Drug discovery classifies atropisomers by barrier (< 84, 84–117, > 117 kJ/mol).

例子Examples

6,6′-二硝基联苯-2,2′-二甲酸(1922 年克里斯蒂与肯纳首次拆分);BINOL 与 BINAP 是不对称催化中最重要的阻转异构配体;万古霉素、某些激酶抑制剂含阻转异构轴。

6,6′-Dinitrobiphenyl-2,2′-dicarboxylic acid (first resolved by Christie and Kenner in 1922); BINOL and BINAP are key atropisomeric ligands in asymmetric catalysis; vancomycin and some kinase inhibitors contain atropisomeric axes.

命名Naming

轴手性用 Rₐ/Sₐ 或 P/M(螺旋方向)表示。

Axial chirality is labelled Ra/Sa or P/M (helicity).

年表Timeline

  • 1922

    克里斯蒂与肯纳拆分取代联苯

    Christie and Kenner resolve a substituted biphenyl

  • 1933

    库恩提出 atropisomer 一词

    Kuhn coins the term atropisomer

  • 1980

    野依等合成 BINAP

    Noyori and co-workers synthesise BINAP