Synthesis of Bridged o-Carboranylphosphine Compounds and the Application in Sterically Demanding Suzuki Coupling Reaction

doi:10.6023/cjoc202601020

Abstract

The synthesis, structures, stabilities of bridged carboranyl-diphenylphosphine compounds and the preliminary applications in metal-catalyzed coupling reactions are reported. The lithium salt of o-carborane reacts with 2-(diphenylphosphino)benzaldehyde to produce bridged diphenylphosphinocarboranylmethanol 1 and bis(diphenylphosphino)-o-carboranylbismethanol 2. The chlorination reaction of compound 1 produces compound 3, and compound 1 undergoes slow oxidation in air to produce the corresponding phosphine oxide compound 4. Compounds 1 and 2 undergo slow oxidation in air, while the oxidation stabilities of the chlorinated compound 3 is significantly higher under the same conditions. Compound 1 readily decomposes into 2-(diphenylphosphine)benzaldehyde and o-carborane under basic conditions, whereas the chlorinated product 3 slowly decomposes under the same conditions. The structures of the products were studied by spectroscopic methods or elemental analysis, single crystal X-ray diffraction (1 and 2) and density functional theory methods (1-3). Compound 3 exhibits potential in palladium catalyzed sterically demanding Suzuki coupling reactions. These results provide new possibilities for bridged o-carboranylphosphine compounds in the catalytic synthesis of organic functional molecules.

Key words: carborane, phosphine compounds, synthesis, stability, Suzuki coupling

Cite this article

Zhang Guoying, Zhang Xueyue, Miao Jinling, Liu Guangning, Wang Bin, Nie Yong. Synthesis of Bridged o-Carboranylphosphine Compounds and the Application in Sterically Demanding Suzuki Coupling Reaction[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202601020.

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