摘要：1 Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science, Rehovot 76100, Israel

转自：康龙化成

Catalytic Oxidation of Carbon–Halogen Bonds by Water with H2

Liberation

Cai You, Lijun Lu, and David Milstein*

1 Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science, Rehovot 76100, Israel

2 Department of Chemistry, School of Sciences, Great Bay University, Dongguan 523000, People’s Republic of China

—J. Am. Chem. Soc. 2025, doi: 10.1021/jacs.5c11295

Recommended by Depei Meng_MC4

KEY WORDS:oxidation,Ru catalysis (反应类型),C(sp3)–C=O (成键),alkyl halides(原料), alkyl carboxylic acids, ketones(产物)

ABSTRACT: The unprecedented catalytic oxidation of carbon–halogen bonds to carboxylic acids using water as the oxidant is disclosed. Compared to previous traditional oxidation reactions, this transformation avoids the use of sacrificial oxidants and liberates useful hydrogen gas as byproduct, presenting an efficient method. Catalyzed by an acridine-based PNP-Ru pincer complex, a series of primary aliphatic and benzylic halides were successfully converted into carboxylic acids in high yields. The oxidation of secondary halides, which yields ketones, was also accomplished efficiently. Moreover, the oxidation of challenging C–F bonds, aliphatic chlorides, and bromides has been achieved for the first time. With further improvement, this method could be effectively utilized in the efficient scale-up synthesis of the phenoxybutyric herbicide, MCPB. Furthermore, a formal anti-Markovnikov oxidation of nonactivated olefins to carboxylic acids has also been demonstrated through a two-step sequence involving anti-Markovnikov hydrobromination followed by oxidation of the resulting alkyl halides.

Oxidation of Carbon−Halogen Bonds

Optimization of Reaction Conditions

Catalytic Oxidation of Primary Alkyl Halides to Carboxylates (selected examples)

Catalytic Oxidation of Secondary Halides to Ketones

Catalytic Oxidation of C−F Bonds

Other Applications (Synthesis of MCPB; Formal Anti-Markovnikov Oxidation of Nonactivated Olefins to Carboxylic Acids)

Proposed Mechanism

In conclusion, Cai You et al.have developed thefirst catalytic oxidation of carbon–halogen bonds using water as the oxidantwith concomitant hydrogen liberation. In contrast to previous traditional oxidation methods, this reaction does not require additional oxidants. A wide variety of primary halides were selectively and efficiently transformed into carboxylates, while secondary halides were converted to ketones. Notably, this method also successfully oxidizes the challenging C–F bonds for the first time.

Cai You等人首次报道了使用水作为氧化剂并伴随氢释放的碳-卤素键催化氧化方法。与之前的传统氧化方法相比，这种反应不需要额外的氧化剂。多种一级烷基卤化物可被选择性且高效地转化为羧酸盐，而二级烷基卤化物则被转化为酮。值得注意的是，这种方法也能成功地实现具有挑战性的C-F键的氧化。

来源：新浪财经