双语化学辞典Chem Lexicon
概念 · 立体化学 · 构象分析 Stereochemistry · Conformational analysis

构象Conformational isomerism

拼音Pinyin gòu xiàng 别名Also 构象异构;conformation; rotamer

定义Definition

构象是分子通过单键旋转而产生的原子空间排列;构象之间的转换不需要断裂化学键,通常能垒很低,室温下快速互变。

Conformations are spatial arrangements reached by rotation about single bonds; interconversion breaks no bonds and usually has low barriers, so conformers interconvert rapidly at room temperature.

能量来源Energy contributions

扭转张力(重叠时键电子对排斥,乙烷能垒约 12 kJ/mol)、空间张力(基团靠得太近)、角张力(小环)以及偶极、氢键作用。布居按玻尔兹曼分布。

Torsional strain (eclipsing bonds; ethane barrier ~12 kJ/mol), steric strain, angle strain (small rings) and dipole or hydrogen-bond interactions; populations follow Boltzmann statistics.

构象分析的意义Why it matters

构象决定反应性(E2 需反式共平面、SN2 的位阻)、生物活性(药物与受体结合的活性构象)和蛋白质折叠。巴顿因构象分析获 1969 年诺贝尔化学奖(与哈塞尔共享)。

Conformation governs reactivity (anti-periplanar E2, SN2 sterics), bioactivity (receptor-bound conformations) and protein folding. Barton and Hassel shared the 1969 Nobel Prize for conformational analysis.

与构型的区别Versus configuration

构型异构(对映、非对映、顺反)必须断键才能转换;构象异构只需绕键旋转。旋转受严重阻碍时可分离出阻转异构体。

Configurational isomers interconvert only by breaking bonds; conformers by rotation. Severely hindered rotation gives separable atropisomers.

年表Timeline

  • 1936

    皮策发现乙烷存在约 12 kJ/mol 的旋转能垒

    Pitzer finds ethane’s ~12 kJ/mol rotational barrier

  • 1950

    巴顿发表甾体构象分析论文

    Barton publishes conformational analysis of steroids

  • 1969

    巴顿与哈塞尔获诺贝尔化学奖

    Barton and Hassel receive the Nobel Prize

相关公式Formulas

卡普拉斯方程 Karplus equation→
\[{}^3J(\phi) = A\cos^2\phi + B\cos\phi + C\]
构象布居(玻尔兹曼) Conformer populations (Boltzmann)→
\[\frac{n_2}{n_1} = \exp\!\left(-\frac{\Delta G^\circ}{RT}\right),\qquad x_i = \frac{e^{-G_i/RT}}{\sum_j e^{-G_j/RT}}\]
例题Worked example

甲基环己烷 A = 7.3 kJ/mol:25 °C 时 K = e^(7300/2478) = 19,平伏键构象占 95%。叔丁基 A ≈ 20 kJ/mol,几乎全部平伏。

Methylcyclohexane A = 7.3 kJ/mol: K = 19, 95 % equatorial at 25 °C. tert-Butyl (A ≈ 20 kJ/mol) is essentially all equatorial.

柯廷–哈米特原理 Curtin–Hammett principle→
\[\frac{[\mathrm{P_B}]}{[\mathrm{P_A}]} = \frac{k_\mathrm{B}}{k_\mathrm{A}}K = \exp\!\left(-\frac{G^\ddagger_\mathrm{B} - G^\ddagger_\mathrm{A}}{RT}\right)\]
例题Worked example

N-甲基哌啶类的 N-烷基化:主要构象未必生成主要产物。

N-alkylation of substituted piperidines: the major conformer need not give the major product.