سنتز كمپلكس هاي CN- اورتوپالاديت و كاربرد آن ها در واكنش هاي جفت شدن كربن-كربن متقاطع و يكسان تحت تابش ريز موج

چكيده انگليسي :

Synthesis of CN Orthopalladated complexes and Their Application in the C C Cross and Homo Coupling Reactions under Microwave Irradiation Fatemeh Rafiee f rafiei@ch iut ac ir September 19 2012 Department of Chemistry Isfahan University of Technology 84156 83111 Isfahan Iran Prof A R Hajipour Email haji@cc iut ac ir Prof A R Dabbagh Email dabbagh@cc iut ac ir Isfahan University of Technology 84156 83111 Isfahan Iran Abstract The palladium catalyzed cross coupling reactions are among the most potent and convenient tools of modern organic synthesis The palladacycle catalysts are the most important classes of catalysts that used as very efficient catalysis with very low concentration in organic synthesis In this thesis the CN orthopalladated complexes have been synthesized using tribenzylamine 2 3 dimethoxy benzaldehyde oxime and 2 3 dimethoxyphenylethaneamine as ligands The activity of these complexes as precatalyst was investigated in various coupling reactions under both conventional and microwave irradiation conditions Substituted biaryls were produced in excellent yields and short reaction times using catalytic amounts of these complexes The best results in Suzuki coupling of aryl halides with aryl boronic acids were obtained in ethanol as the solvent and K2CO3 as base at 60 C Stille reaction of various aryl halides with phenyltributyltins were carried out using these ortho palladated complexes in DMF as solvent and K2CO3 as base at 100 C Hiyama cross coupling reaction of various aryl halides with triethoxy phenyl silane were created the corresponding products in excellent yields in DMF as solvent and TBAF as base and additive at 90 C The symmetrical biaryls were obtained via homo coupling reaction of various aryl halides in NMP as the solvent and K2CO3 as base at 130 C The CN orthopalladated complexes were applied successfully in the Heck cross coupling reaction of different types of aryl halides and also arenesulfonyl chlorides with various olefines in NMP as the solvent and K2CO3 as base at 130 C The catalytic activity of these complexes was investigated in Sonogashira cross coupling reaction under copper free conditions Various aryl halides were efficiently coupled with phenylacetylene in the mostly moderate to good yields in NMP using piperidine as base at 100 C Also an efficient methodology was reported for the preparation of substituted benzonitriles from various aryl halides using CN orthopalladated complexes as precatalyst and K4 Fe CN 6 The catalytic amounts of these complexes caused to produce aryl nitriles in DMF as solvent K2CO3 as base and TBAB as promoter at 130 C Microwave irradiation in comparison to conventional reflux conditions led to dramatically reduced reaction times and higher yields The monomeric complexes had been demonstrated to be more active than the corresponding dimeric catalyst dimer for the cross coupling of unreactive aryl chlorides The activity of dimeric CN orthopalladate complex of homoveratrylamine was investigated in the Heck Mizoroki coupling reaction under conventional heating and microwave irradiation conditions in molten salt tetrabutylammonium bromide as the solvent and promoter at 130 C This complex in these conditions is an active and efficient catalyst for the Heck reaction of different types of aryl halides Keywords Homogeneous catalysts orthopalladated complexes coupling reaction microwave irradiation

رفيعي، فاطمه

سنتز كمپلكس هاي CN- اورتوپالاديت و كاربرد آن ها در واكنش هاي جفت شدن كربن-كربن متقاطع و يكسان تحت تابش ريز موج

كاتاليزور همگن , پالاداسيكل , تابش ريز موج