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3.4.1.3.4 Method 4: Biaryl Syntheses from Aryl Halides and Copper(I) Salts

DOI: 10.1055/sos-SD-003-00274

Heaney, H.; Christie, S.Science of Synthesis, (20043361.

Ullmann-type coupling reactions have also been reported in reactions using aryl iodides and copper(I) trifluoromethanesulfonate [copper(I) triflate]. For example, when an acetone solution of 1-iodo-2-nitrobenzene and copper(I) triflate is treated with an equal volume of 5% aqueous ammonia solution, the reaction is complete at room temperature in five minutes and gives 2,2-dinitrobiphenyl in ca. 90% yield.[‌406‌] The efficient reductive coupling of aryl iodides has also been carried out using using copper(I) thiophene-2-carboxylate, e.g. to give 26. Whereas with benzenoid derivatives the presence of an ortho-ligating group is required, this is not the case with 2-iodo heteroaromatic substrates.[‌407‌] Examples are shown in Scheme 76. The Ullmann-like coupling of 1,2,4,5-tetrafluoro-3,6-diiodobenzene has also been carried out at room temperature in N-methylpyrrolidin-2-one in the presence of copper(I) thiophene-2-carboxylate. Mixtures of poly(para-tetrafluorophenylene) derivatives are obtained that contain up to five benzenoid rings.[‌408‌]

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Meeeeeeeeeee Meeeeeeee

M,M-Meeeeeee-8,8,8,8,8,8-eeeeeeeeeee-8,8-eeeeeeee-8,8-eeeeeee (88); Meeeeee Meeeeeeee:[‌888‌]

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References