jo982494c_si_001.pdf (965.47 kB)
Cesium Fluoride Catalyzed Trifluoromethylation of Esters, Aldehydes, and Ketones with (Trifluoromethyl)trimethylsilane
journal contribution
posted on 1999-03-31, 00:00 authored by Rajendra P. Singh, Ganfeng Cao, Robert L. Kirchmeier, Jean'ne M. ShreeveThe low reactivity of carboxylic esters toward (trifluoromethyl)trimethylsilane (TMS−CF3) was
investigated. A universal cesium fluoride catalyzed procedure for nucleophilic trifluoromethylation
was developed. At room temperature (25 °C), with catalytic amounts of cesium fluoride, carboxylic
esters were found to react to give the silyl ether intermediates, which afforded the trifluoromethyl
ketones after hydrolysis. Sulfonic, sulfinic, and selenic esters also show good reactivity, giving novel
trifluoromethylated compounds. The trifluoromethylation method was also applied to aldehydes
and ketones, which were transformed to trifluoromethyl silyl ether intermediates and afforded
trifluoromethylated alcohols in excellent yields after acid hydrolysis. Ethylene glycol dimethyl ether
was used as solvent for solid or high boiling substrates, and benzonitrile was used for the low
boiling substrates.