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Development of palladium catalyzed methodology to synthesize alpha-substituted alpha,beta-unsaturated carbonyl derivatives

Purdue University
Publication Date
  • Chemistry
  • Organic


A novel and highly selective methodology based on palladium catalyzed cross coupling of either α-halo-α,β-unsaturated carbonyl compounds or the corresponding α-metallo derivatives was developed. Simple alkyl, homoallyl, homopropargyl, benzyl, aryl, and alkenyl groups could be introduced into the α-position of 2-iodocyclohexenone and 2-iodocylopentenone. The yields ranged from good to acceptable. In order to find the optimal conditions, a systematic screening of palladium catalysts as well as generation methods of the organometals were conducted. The synthesis of 3-substituted-2(5H)-furanones through Pd-catalyzed carbonylation of (Z)-3-Iodo-3-substituted-2-propen-1-ol was fully developed. 3-Phenyl-5,6-dihydropyran-2-one was also synthesized through the modified acylpalladium process. The application of this method in the synthesis of hamabiwalactone-B was very successful. The synthetic conditions of 1,5-dienes were optimized. Pd(PPh3)4 was capable to promote the alkenyl-homoallyl and aryl-homoallyl cross-coupling reactions and give good yields in most cases. In more demanding cases, Pd(dppf)Cl 2 would be an optimal catalyst. ^

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