Synthetic method and application of novel multi-aryl bridged long-chain diphosphine ligand

Abstract

A novel multi-aryl bridged long-chain diphosphine ligand is disclosed. A semi-calix[4]arene is taken as a structural skeleton and subjected to double-side decoration, so that a novel phosphine-nitrogen ligand is designed and synthesized, and also the novel ligand and a palladium salt are used for in-situ catalysis of a Suzuki coupling reaction. The preparation method of the ligand comprises: synthesizing a semi-calix intermediate bis(5-tert-butyl-3-hydroxymethyl-2-methoxyphenyl)methane, brominating the intermediate and bridging with an intermediate 2-bromo-6-diphenylphosphanylpyridine to obtain the multi-aryl bridged long-chain diphosphine ligand. The advantages comprise that the novel diphosphine ligand employs the calixarene fragment as the main body, pyridine structure is used to stabilize the molecule and to adjust the molecular cavity, and the ligand is used to catalyze the Suzuki coupling reaction in the presence of trace palladium for carbon-carbon bond construction in organic synthesis. The ligand is stable in structure; the synthesis reaction is short in time, mild in condition, high in yield, easy for mass production and commercialization; and the catalyst use amount is small when the ligand is used for Suzuki coupling reactions, and it is expected that functional groups with specific function can be introduced for promoting synthesis of multiple medicaments.

Description

【Technical field】 [0001] The invention relates to the preparation of catalyst ligands for cross-coupling reactions, especially a novel polyaryl-bridged long-chain diphosphine ligand bis[3-(6-(2-diphenylphosphino))pyridine Methylene base)-5-tert-butyl-2-methoxyphenyl] methane synthesis method and application in organic synthesis catalysis. 【Background technique】 [0002] Transition metal-catalyzed coupling reactions have important applications in the field of organic synthesis. At present, palladium-catalyzed cross-coupling reactions mainly include: Heck reaction-C-C coupling between halogenated aromatics and alkenes; Negishi reaction-C-C coupling between halogenated aromatics and organozinc reagents; Suzuki reaction-halogenated aromatics C-C coupling with organic boronic acid; Sonogashira reaction - C-C coupling between halogenated aromatic hydrocarbons, halogenated alkenes or trifluoroester compounds and sp-type terminal alkynes. Suzuki coupling reaction has obvious advan...

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Problems solved by technology

[0005] In terms of catalytic applications, the currently reported phosphine ligands supported by calixarene platforms are mainly used in catalytic hydroformylation, asymmetric hydrogenation, olefin polymerization, etc. The design of such phosphine ligands has not been reported in the review

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