Synthesis of -Cyano Ketones Promoted by a Heterogeneous Fluoride Catalyst

ADVANCED SYNTHESIS & CATALYSIS

卷 358, 期 13, 页码 2134-2139

WILEY-V C H VERLAG GMBH

-cyano ketones; heterogeneous catalysis; solvent-free conditions; sustainable chemistry; A simple protocol for the conjugate addition of cyanide group to; -unsaturated ketones has been developed; By exploiting solvent-free conditions; the use of Amberlist-F (Amb-F) as heterogeneous fluoride catalyst; and trimethylsilyl cyanide (TMSCN) as reactant; -cyano ketones have been obtained in good to excellent yields (73-99%) and with a low E-factor value (9-22); By the same procedure a representative cyano oxazolidinone and a cyano ester have been also prepared; The direct recovery and reuse of Amb-F in the -cyanation process has been approached but proved to be impossible; As an alternative; a two-step protocol based on two different catalysts has been defined; Polystyryl-diphenylphosphine (PS-TPP) has been used for promoting the kinetic 1; 2-addition affording a cyanohydrin trimethylsilyl ether; and Amb-F to promote a cyanide group 1; 2-1; 4-shift to obtain the -cyano ketone; In this manner the recycling of both catalysts is possible; Further optimization of the two-steps protocol led to to very low E-factor values (0; 8-1; 3)

Chemistry, Applied Chemistry, Organic

1. Universita degli Studi di Perugia
2. MIUR [PGR123GHQY]