パラジウム触媒を用いたアリールアミン類と2-ブロモ-3,3,3-トリフルオロプロペンとのカップリング反応

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The palladium-catalyzed coupling of arylamines and 2-bromo-3,3,3-trifluoropropene (BTP) was investigated. When a toluene solution of aniline and BTP was heated to 110℃ in the presence of Pd_2(dba)_3-CHCl_3, 1,1'-diphenylphosphinoferrocene and Cs_2CO_3 in an argon atmosphere, N-(1,1,1-trifluoro-2-propylidene)aniline was obtained with an excellent ^<19>F-NMR yields (99 %) and isolated yield (92 %). Cs_2CP_3 was exclusively effective in the coupling. The coupling using 2-aminobenzonitriles as substrates provided not only 2-N-(1,1,1-trifluoro-2-propylidene)aminobenzonitriles but also 4-amino-2-trifluoromethylquinolines and 2-trifluoromethyl-4-N-(1,1,1-trifluoro-2-propylidene)aminoquinolmes. The strong electron withdrawing character of CF_3 will enhance the acidity of the methyl proton in the N-(1,1,1-trifluoromethyl-2-propylidene)amino group, resulting in the addition of the methyl proton to the carbon in the cyano group and cyclization to 4-amino-2-trifluoromethylquinolines. Moreover, the one-pot synthesis of 2-trifluoromethylindoles with 2-bromoanilines and BTP was achieved using Pd(OAc)_2, 2-dicyclohexyl-2',4',6'-triisopropylbiphenyl and Cs_2CO_3. The Pd-catalyzed intramolecular Heck coupling of the vinyl group in 2-bromo-N-(1-trifluoromethyl)vinylanilines, which is the tautmeric isomer of 2-bromo-N-(1,1,1-trifluoro-2-propylidene)anilines, and the C-Br bond presumably furnished indole rings. C-N double bond of the N-(1,1,1-trifluoro-2-propylidene)amino group obtained here was smoothly hydrogenated to the N-(1-methyl-2,2,2-trifluoro)ethylamino group using LiAlH_4 or H_2 with Pd/C.
東海大学の論文

パラジウム触媒を用いたアリールアミン類と2-ブロモ-3,3,3-トリフルオロプロペンとのカップリング反応

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