Synthesis of β‐Cyano Ketones Promoted by a Heterogeneous Fluoride Catalyst期刊界 All Journals 搜尽天下杂志传播学术成果专业期刊搜索期刊信息化学术搜索

Synthesis of β‐Cyano Ketones Promoted by a Heterogeneous Fluoride Catalyst

Authors:	Giacomo Strappaveccia Tommaso Angelini Luca Bianchi Stefano Santoro Oriana Piermatti Daniela Lanari Luigi Vaccaro

Abstract:

Keywords:	β ‐cyano ketones heterogeneous catalysis solvent‐free conditions sustainable chemistry A simple protocol for the conjugate addition of cyanide group to α β ‐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 β ‐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 β ‐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 β ‐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)