Cationic(η3-Allyl) Palladium Complexes Bearing Fluoro-ponytailed Bipyridine ligands-catalyzed Mizoroki-Heck Reaction under Thermomorphic Mode(or in Microwave Reactor)

• Main Authors: Chieh-Keng Li, 李杰耕
• Other Authors: Norman Lu
• Format: Others
• Language: zh-TW
• Published: 2010
• Online Access: http://ndltd.ncl.edu.tw/handle/j42mf9

碩士 === 國立臺北科技大學 === 有機高分子研究所 === 98 === The reaction of allylpalladium(II) chloride dimer and [4,4′-bis(RfCH2OCH2)-2,2′-bpy, 1a-c, Rf= C9F19 (a), C10F21 (b), C11F23 (c)] in the presence of AgOTf (OTf= CF3SO3) resulted in cationic complexes, [Pd(η3-allyl)(4,4′-bis-(RfCH2OCH2)-2,2′-bpy)](OTf), 2a-c, respectively. Complexes 2a-c, obvious soluble in polar organic solvents at 10~45℃but insoluble at －20~－30℃, were demonstrated as catalysts in the cationic Pd-catalyzed Heck reaction under the thermomorphic mode and recovered for reusage. The cationic Pd-catalyzed Heck arylation of methyl acrylate with aryl bromides was selected to demonstrate the feasibility of recycling usage with 2b as the catalyst using DMF as the solvent at 150℃ for about 15 h in each run. At the end of each cycle, the product mixtures were cooled to －20℃; then catalysts were recovered by decantation. The products were quantified by GC analysis and yield was about 90~100% . The Heck reaction of C6H5I with methyl acrylate could be catalyzed by 2b with good recycling results for a total of 15 times.