0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest.
Please login or sign up for a free trial to access the full content. 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]

Meeeee 88 Meeeeee Meeeeeeee Meeee Meeeee(M) Meeeeeeee-8-eeeeeeeeeee[‌888‌]

Meeeeeeee eeee eeeeeee eeee eeeeeeeee eeee eeee eeeeeeeee Meeeeee eeeeeeeee eeeee ee eeeeeeeee eeeeeeee ee eeeeee(M) ee eee eeeeeee ee eee eeeee eee eeee eeeeeeeee eeeeeee ee eee ee e eeeeee(MMM) eeeeeeeeeeee.[‌888‌] M eeeeeee ee eeeeeeee eee eeee eeeeeeee, eeee ee eeeee eeeeeeee eee eeeeeeeeeeee ee eeee eeeeeeee ee eeeeeeee. Meeeeee eeee eeeeee eeee eee eeeeeeeee eee eeeeee eeeee ee eeee eeeeeee eee eeeee eeeee ee eee eeeeee(M) eeeeeee. Mee eee eeee ee eee eeeeeeeee eeeeeee eee ee eee eeeeeeee ee eeeeeee eeeeeee ee eeeeeee ee ee eee eeeeeeeee ee e eeeeee(M)eeeeeee eeeeeee.[‌888‌] Meeeeeee eee eeeeeeee eeeeeeeeee eeee ee eee eeeeeeeee Meeeeee eeeeeeee eee eeeee eeeeeeeee, eeeee eee e eeeeee ee eeeeeeee eeeeeeeeeeee. Meee eeeeeee ee eee ee ee eeeeeeeeeeee eeee eee ee eeeeeeeeee, eee eeeeeeeeee eeeeeeee eee eee eeeeee ee eee eeee, eee eeee-eeeeeee eeeeeeeeeee eee ee eeeeeeee. M eeeeeeee eeeeeeeeeee eeeeeeee eee eee eeeeeeeee eeeeeee eee eeeee eeeeeee eeeeeeeeee ee eeeee ee Meeeee 88.

Meeeee 88 Meeeeeee Meeeeeeeeee Meeeeeee eee e Meeeee(MMM) Meeeeeeeeeee

Meeeeee, eee eeeeeee eeee eeeeeeeeee eee eeeeeeeee ee eee eeeeeeeee Meeeeee eeeeee eeeeeeeee ee eeee e eeeeeeeeeee eeeeee ee eeee eeeeeee eeeee eeeeeeeee eeeeeeeee eeeeeee eee eeeee eeeeeeee eeeeee, eeeeeeeee ee eee eeeeeeee ee e eeeeeee eeee ee eeeeeeee ee eeeeeeeeeeeeeeeee, eeee eeeeeee eee ee eeeeeeeeee(M) eeeeeeeeeeee, eee eeeeeeeee eeeeeee eee ee eeeeeee eeeeeeeee. Mee eeeeeeeeee(M) eeeeeee eee eeee eeeeeeee eeee eee eeeeeeeee ee eeeeee(8) ee eeeeee eeee e eeeeee eeeeeeee ee eeee eeeeee eeee eee eeeeeeeee ee eeeeee(M) eeeeee. Me ee ee eeeeeeee ee eeee eeee eeeeeee eee eeeeeeeeeeee ee eeeeeeeee(eeeeee)eeeeee ee eeeeee(M) eeeeeeee ee eeeeeeee eeeeeeeee ee eeeeeeeeeeeeeeeee eeeee ee eee eeeeeeeee ee eeeeeeee ee 88% eeeee, e eeeeeee eeeeeeee eeeee eeeeee(eeeeeeee)eeeeeeeeeeee ee eee eeeeee eeeee eeee e eeeee ee eeeeeeee.[‌888‌] Me eee eeeee eeee, eeee eeeeee(eeeeeeee)eeeeeeeeeeee ee eeeeeee eeee 888eee% ee eeeeeeeeeeeeeeeeee eeeeeeee ee eeeeeeeeeeeeeee ee eee eeeeeeee ee 8eee% ee eeeeee(M) eeeeee, eeeeeeee ee eeeeee ee 88% eeeee eeeee e eeeeeeee eeeeeeeee eee eeee eeee eeeeeee. Me e eeeeeee eeeeeeee, eeeeee(eeeeeeee)(8-eeeeeee)eeeeee eeeee 8,8-eeeeeeeee ee 88% eeeee.[‌888‌] Me ee eeee eeeeeeeeeee ee eeee ee eeee eeeee eeee eeeeeeeeeee eeeeee eeeeeeeeeee eeee eeee eeeeeeee ee eeeeeeeeee eeeeee ee eeeeeeeee ee eeeeeeeeeeeeeeeeeeeee eeee eeeeee(MM) eeeeeee.[‌888‌] Mee eeeeeeeee ee eeeeeee eee eeeee-eeeeeeee eeeeeeeee eee eeee eeee eeeeeeee. M eee eeee ee eee eeeeeeeee ee eeeeeeeeeeeeee, e eeeeeeeeee eeeeeeeeeee ee e eeeeeeeeeee eeeeee eeeeeeee eeee eee eeeeee eeeeeeeeeeeeee eeeeeeee, eeeeeeee eee eee ee eeeeee(M) eeeeeee ee eeeeeeee ee eeeeeeee(eeeeeeeeeeeeeeeeee)eeeeeeeee eee eeeeeee eeeeeeee. Mee eeeeeeee eeeeeeee ee M-(eeee-eeeeeeeeeeeeeeee)-8-(eeeeeeeeeeeeeeee)eeeeeee eeee 8-eeeee-8,8-eeeeeeeee-8-[(eeeeeeeeeeeeeeeeeeeeeeee)eee]eeeeeeeee eeeee eeeee eeeeeeee eeeee eee eeeeee, 8-eeeee-8-[8-[(eeee-eeeeeeeeeeeeeeee)eeeee]eeeeee]-8,8-eeeeeeeeeeeeeeeeee, ee 88% eeeee.[‌888‌] Meeeeeeee, eeeeeeeeeee ee eeeeee(M) eeeeeee ee eeeeee eee eeee eeee eeeeeeeeeeee ee eee eeeeeeeee-eeeeeeeee eeeeeeeee ee eeeeeeee eeeeeeeee eee eeeeeeeeee ee eeeeeeeee ee eeee eeeeeeeeeeeeeeeeeeeeeeeee eeee eeeeeeee(eeee)eeeeeeeee[‌888‌] eee ee eeeeeeeee ee 8-(eeeeeeeeeeeeee)-8,8,8-eeeeeeee eeee e eeeeee ee eeee eeeeeeeeeeeeeeeee.[‌888‌] Me eee eeeeeeeee ee ee eeeee eeeee eeee eeeeeeeee(M) eeeeeeeeeeeeeee ee eeeeeeee ee eee eeeeeeeee.[‌888‌] Mee eeeeee ee eeeee eeeeee(M) eeeeee ee eee eeeeeeee ee e eeeeeee Meeeee eeeeeeee eeeeeeee eeeee eeeeeeeee eeeeeee eee eeee eeeeeee.[‌888‌] Meeeeeee eee eee ee eeeeee(M) eeeeee eee eeeeee eeeeee eeee eeee ee eeeeeeeeeee eeee e eeee eeeeee eeee ee eeeeeeeeeeeeeee, eee eee ee eeeeeeeeeeeeeeeeee ee eee eeeeeeeee eeeeee eeeeeee ee e >888-eeee eeee eeeeeeee eeeeeeee ee eee eeee eeeee e eeeeeee Meeeee eeeeeeee. Meee eeeee eeee eeeeee eeee eeeeee(M) eeeeee ee e eeee eeeeeeeee eee eeee eeeeee eee ee eeeeeeee eeee eeeeeeee eee eeeeeee eeeee eeeeeeeee eeee eeeeeeeeeeee eeeeeee eee eeeeeeee eeee eee eeee eeeeeeeeeeeeee ee eeeeeeeee(MM) eeeeeee. Meeeeeee eeeeeee eeee eeee eeee eeeeeeee ee eeeeeeeee-eeeeeeeee Meeeee eeeee-eeeeeeee eeeeeeeee ee eeeeeeeeeee eeeee eeeee eeeeee eeeeeeeeeee eeee ee eeeeee(M) eeeeee,[‌888‌] eeeeee(M) eeeeeeeee-8-eeeeeeeeeee,[‌888‌] eee eeeeee(M) 8-eeeeeeeeeeeeeeee.[‌888‌] Meee ee eeeeeeeee eeeeee eeee eeee eeeeeeee ee eeeeeeeee eeee eeee eeeeeeeee eeeeee eeeeeeeeeeee ee eeeeeeee eeeeeeeee ee eeeeeeeeeeeee eeee eeee e eeeeee ee eeee- eee eeeeeeeeeeee eeeeeeeeeee.[‌888‌]

M eeeee eeeeeeeeeee ee eeee eeeeeeee eeeeee eeeeee ee eee eeeeee eeeeeee. Meeeeee eeeeeeee ee eeeeeeeeeee ee e eeeeeeeeeeee eeeeeeee eeeeee eeee 888% eeeeeeeeeee eeeee eeeee-eeee-eeeeee eeeeeeeeee,[‌888‌] eee eee eeeeeeeeee eeee eeee eeeeeeeee.[‌888‌] Me eee eeeeeee eeeeeeee (<8 eeeeeeeee), ee eeeee 888M, eeeeeeeeeee eeeeeeeeeee ee eee Me(MMM) eeeeeee ee eeee eeeeeeee eeeeee eeeeee eeeee eeee eeeeee ee eeee eeeeeeee ee 888888M. Me eeee eeeeeee eeeeeeee (88 eeeeeeeeee), eeeeeeee ee eeeeee ee eeeee 888M ee e eeeeee eeeeeee eeee eeeeeeee eee eeeeeeee ee eeeeeeee eeeeee eeeeee eeee eeeeeeeeeee.

Meeeeeeeeeee Meeeeeeee

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

Meeeee(M) eeeeeeeee-8-eeeeeeeeeee (8.88e, 8.8eeee) eee eeeee ee eee eeeeeee ee M-eeeeee-8-eeee-8,8,8-eeeeeeeeeeeeeeeee (8.88e, 8.8eeee) ee MMM (8eM) eeeee M8. Meeee eeeee eeeeeee ee ee eee 8e, eee eeeeeee eee eeeeeee eeee MeMMe (88eM) eee eee eeeeeeeee eeeeee eee eeeeee eeeeeee e eeee ee eeeeee eee eeeee MeMMe ee eee eeeeee (888eM). Mee eeeeeeee eeee eeee eeeeeee ee eeeeee eeeeeeeeeee eee eeeeeee ee eeeeee eeeeeeeeeeee. Meeeeeee MMM eee eeeeeee eeeee eeeeee ee ee eeeeeeeee. Mee eeeee eeeeeee eee eeee eeeeeeeee ee MM8Me8 (8eM) eee Me8M (88eM) eee eee eeeeee ee eeeeeeee eee eeeeeee ee 88% eee eeee eeeeee (8eM) eee eeeee. Mee eeee eee eeeeee ee e eeeeeee eee ee eee eeeee eeeee eee eeeeee eeeee eee eeeee ee ee 88; eeeee: 8.888e (88%); ee 888888°M (Me8M/eeeeee).