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2.6.1.4.1 Copper-Mediated Nucleophilic Trifluoromethylation of Alkynes with Ruppertʼs Reagent

DOI: 10.1055/sos-SD-213-00216

Lishchynskyi, A.; Novák, P.; Grushin, V. V.Science of Synthesis: C-1 Building Blocks in Organic Synthesis, (20142402.

Copper-mediated aerobic oxidative trifluoromethylation of terminal alkynes with Ruppertʼs reagent [trimethyl(trifluoromethyl)silane] in excess proceeds at elevated temperatures with a broad variety of substrates to give the desired products 34 in moderate to good yields (Scheme 20).[‌102‌] The reaction is performed on up to a 10-mmol scale. To conduct the reaction in a catalytic manner, both the substrate and a portion of trimethyl(trifluoromethyl)silane should be added slowly using a syringe pump.[‌74‌] The catalytic reaction is higher yielding for the 3-nitrophenyl substrate. A smaller, twofold excess of trimethyl(trifluoromethyl)silane can be used with silver(I) carbonate as the oxidant, and the reaction readily occurs at room temperature under such conditions.[‌103‌] In a lower-cost alternative, pure oxygen in combination with molecular sieves can be used (Scheme 21).

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M8 Meeeeeee Meeee (eeee) Meeeeee Meeee (%) 88M MMM (δ) Mee
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