双语化学辞典Chem Lexicon
反应 · 有机化学 · 氧化反应 Organic chemistry · Oxidations

贝耶尔-维利格氧化Baeyer–Villiger oxidation

拼音Pinyin bèi yē ěr wéi lì gé yǎng huà　别名Also 拜耳-维利格氧化； Baeyer–Villiger rearrangement

定义Definition

贝耶尔-维利格氧化是用过氧酸（如间氯过氧苯甲酸 m-CPBA）或过氧化氢把酮转化为酯（环酮转化为内酯）的反应，相当于在羰基与一个相邻碳之间插入一个氧原子。

The Baeyer–Villiger oxidation converts ketones into esters (cyclic ketones into lactones) with peracids such as m-CPBA or with hydrogen peroxide, inserting an oxygen atom between the carbonyl and an adjacent carbon.

机理Mechanism

过氧酸加成到羰基形成克里吉中间体；随后一个烷基带着电子对从碳迁移到相邻的氧上，同时羧酸根离去（协同步骤）。迁移基团的构型保持不变。

The peracid adds to the carbonyl to form the Criegee intermediate; one group then migrates with its electron pair from carbon to the adjacent oxygen as the carboxylate leaves (concerted). The migrating group keeps its configuration.

迁移顺序Migratory aptitude

叔烷基 > 环己基 ≈ 仲烷基 ≈ 苄基 ≈ 苯基 > 伯烷基 > 甲基，即更能稳定正电荷的基团优先迁移。醛中 H 迁移最快，得到羧酸。

Tertiary alkyl > cyclohexyl ≈ secondary ≈ benzyl ≈ phenyl > primary > methyl — groups that better stabilise positive charge migrate first; in aldehydes H migrates, giving acids.

由来与应用Origin and uses

阿道夫·冯·贝耶尔与维克托·维利格于 1899 年用卡罗酸（过一硫酸）报道。工业上由环己酮制 ε-己内酯（聚己内酯原料）。生物体内黄素依赖的贝耶尔-维利格单加氧酶可高对映选择性地完成此反应。

Reported in 1899 by Adolf von Baeyer and Victor Villiger using Caro’s acid. Industrially it converts cyclohexanone into ε-caprolactone (for polycaprolactone). Flavin-dependent Baeyer–Villiger monooxygenases perform it enantioselectively.

反应Reactions

R–CO–R′ + R″CO3H ⟶ R–CO–O–R′ + R″CO2H

m-CPBA/CH₂Cl₂，0 °C 至室温；或 H₂O₂ 与路易斯酸（Sn-β 分子筛）

m-CPBA in CH₂Cl₂ at 0 °C to room temperature, or H₂O₂ with a Lewis acid (Sn-beta zeolite)

  1. 过氧酸加成到羰基生成克里吉中间体。

    The peracid adds to form the Criegee intermediate.

  2. 取代基迁移到氧上，羧酸根离去。

    A substituent migrates to oxygen as the carboxylate departs.

  3. 失去质子得酯。

    Deprotonation gives the ester.

环己酮 + m-CPBA ⟶ ε-己内酯Cyclohexanone + m-CPBA ⟶ ε-Lactone

扩环成七元内酯。

Ring expansion to a seven-membered lactone.

反应机理图Mechanism

红色弯箭头表示一对电子的移动方向：从电子来源（孤对电子或化学键）指向电子去向。Red curly arrows show where an electron pair moves: from its source (lone pair or bond) to its destination.

1

过氧酸加到酮羰基上

The peroxy acid adds to the ketone carbonyl

质子转移H⁺ shift
2

克里吉中间体：一个烷基迁移到氧上，羧酸根离去

Criegee intermediate: an alkyl group migrates to O as carboxylate leaves

3

酯；迁移能力：叔烷基 > 仲烷基 ≈ 苯基 > 伯烷基 > 甲基

Ester; migratory aptitude 3° alkyl > 2° ≈ phenyl > 1° > methyl

年表Timeline

  • 1899

    贝耶尔与维利格报道

    Baeyer and Villiger report it

  • 1948

    克里吉提出四面体中间体机理

    Criegee proposes the tetrahedral-intermediate mechanism