パラジウム-水溶性ホスフィン錯体による二相系触媒反応

概要

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Water-soluble complex catalysts are useful because of simple separation from the products, high activity, and selectivity. To conduct palladium-catalyzed reactions under liquid-liquid two-phase conditions, water-soluble polyether- or crown ether-substituted phosphines with phase transfer ability have been synthesized and characterized. The following reactions in aqueous media catalyzed by the water-soluble phosphine complexes of palladium are surveyed. (1) Hydrogenolysis of allylic halides with formate proceeds smoothly under liquid-liquid or liquid-solid two-phase conditions and 1-olefins are formed. In the two-phase catalysis the palladium complex itself plays a role of a phase transfer agent and a mechanism of inverse phase transfer process has been proposed. Benzylic halides are reduced similarly. (2) Allylic and benzylic halides are carbonylated under atmospheric pressure in aqueous NaOH/organic solvent system to afford β, γ-unsaturated acid and phenylacetic acid, respectively. (3) The reaction of bromoarenes possessing electron-withdrawing groups with ethylene (the Heck reaction) is also possible in an aqueous phase.
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