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. 2011 Apr 11;50(16):3793-8.
doi: 10.1002/anie.201100633. Epub 2011 Mar 25.

A broadly applicable copper reagent for trifluoromethylations and perfluoroalkylations of aryl iodides and bromides

Hiroyuki Morimoto  1 , Tetsu Tsubogo, Nichole D Litvinas, John F Hartwig
Affiliations

A broadly applicable copper reagent for trifluoromethylations and perfluoroalkylations of aryl iodides and bromides

Hiroyuki Morimoto et al. Angew Chem Int Ed Engl. .
No abstract available

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Figures

Scheme 1
Scheme 1
Synthesis of 1,10-phenanthroline-ligated (perfluoroalkyl)copper(I) complexes 1 and 2.
Scheme 2
Scheme 2
Reactivity of complex 1 with 5 equivalents aryl iodide 3 at room temperature. Yield was determined by 19F NMR analysis with 4-CF3OC6H4OMe as internal standard. The yield was reported as an average of two runs. Yield of 4b in parentheses was obtained from the reaction with complex 1 stored over 1 month under nitrogen atmosphere.
Scheme 3
Scheme 3
Reactivity of complex 1 with 5 equivalents aryl bromide 5 at 110°C.
Scheme 4
Scheme 4
Copper-mediated trifluoromethylation with isolated (trifluoromethyl)copper(I) complex 1. The reactions were conducted with 0.50 mmol aryl iodide 3 and 0.75 mmol 1 in DMF (0.25M) at 50°C; yields of isolated products are reported unless otherwise noted. The reactions of 3 c, 3 e and 3 bb were run on a 0.10 mmol scale. [a] The yield was determined by 19F NMR spectroscopy with 4-CF3OC6H4OMe as internal standard. [b] The reaction was performed with 1 that was weighted in air. [c] The reaction was performed at room temperature. [d] The reaction was performed with 1.2 equivalents 1 at room temperature. [e] 3.0 equivalents 1 was used.
Scheme 5
Scheme 5
Copper-mediated trifluoromethylation with (trifluoromethyl)copper complex 1 generated in situ. All reactions were performed with 0.50 mmol haloarene as limiting agent without the use of a glove box unless otherwise noted. [a] The reaction was conducted with 1.5 equivalents 1 prepared in situ. [b] The reaction was conducted with 10 mmol iodoarene for 24 h. [c] The yield was determined by 19F NMR spectroscopy with 4-CF3OC6H4OMe as internal standard.
Scheme 6
Scheme 6
Comparison of the reactions of aryl iodides 3. The yields were determined by 19F NMR spectroscopy with 4-CF3OC6H4OMe as internal standard.
Scheme 7
Scheme 7
Comparison of the reactions of aryl bromides 5. The yields were determined by 19F NMR spectroscopy with 4-CF3OC6H4OMe as internal standard.
Scheme 8
Scheme 8
Perfluoroalkylation of aryl iodides 3. The reaction was performed with 1.5 equivalents 2 at 50°C unless otherwise noted. [a] The reaction was conducted at 80°C with perfluoropropylcopper complex 2 prepared in situ under the same conditions as for reactions in Scheme 5. [b] The reaction was performed at room temperature.
Scheme 9
Scheme 9
Trifluoromethylation of 2-(allyloxy)iodobenzene. Trifluoromethylarene 4 cc was obtained in 91% yield; cyclized product 7 was not detected by GC-MS analysis.
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References

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    1. For recent developments in trifluoromethylation of arenes, see: Ball ND, Kampf JW, Sanford MS. J Am Chem Soc. 2010;132:2878–2879.Wang XS, Truesdale L, Yu JQ. J Am Chem Soc. 2010;132:3648–3649.

    1. For recent developments in trifluoromethylation of aryl boronic acids, see: Senecal TD, Parsons AT, Buchwald SL. J Org Chem. 2011;76:1174–1176.Chu L, Qing FL. Org Lett. 2010;12:5060–5063.

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