The Stille coupling reaction of aryl triflates with n-tributylallenyl stannane : a general route to arylallenes

Palladium-Catalyzed Amination of Aryl Triflates and Importance of Triflate Addition Rate

“…Pd(dba) 2 was prepared by literature procedures . The aryl triflates were prepared according to the methods of Stille 12 and have been prepared previously: 4-methoxyphenyl, 2-naphthyl, 4-cyanophenyl , 4-benzoylphenyl, 4-phenylphenyl, 2-methylphenyl, and 4-methylphenyl …”

“…Pd-(dba)2 was prepared by literature procedures. 23 The aryl triflates were prepared according to the methods of Stille 12 and have been prepared previously: 4-methoxyphenyl, 12 2-naphthyl, 11 4-cyanophenyl 24 , 4-benzoylphenyl, 15 4-phenylphenyl, 25 2-methylphenyl, 26 and 4-methylphenyl. 11 Reactions were set-up in an inert atmosphere glove box, although it is equally effective to simply degas solvents before conducting the reactions under a nitrogen atmosphere.…”

“…1 H NMR: (CDCl3) δ 3.41 (s, 3H), 6.80 (d, 8.9 Hz, 2H), 7. 25 N-Phenyl-2-naphthylamine (Table 1, entry 6). Using the general procedure for anilines with 66.8 mg (0.242 mmol) of 2-naphthyl triflate and 30.0 µL (0.329 mmol) of aniline yielded the product as a white solid (52.3 mg, 99%), whose NMR spectra were identical to commercial material available from Aldrich.…”

“…General procedure B with 150 mg (0.50 mmol) of 4-biphenylyl triflate and 79.0 µL (0.75 mmol) of piperidine gave the product as a white solid (78.8 mg, 67% yield). 1 H NMR: (CDCl3) δ 1.61-1.68 (m, 2H), 1.72-1.82 (m, 4H), 3 25. 3.33 (m, 4H), 7.00 (d, 8.5 Hz, 2H), 7.27 (d, 7.5 Hz, 1H), 7.42 (t, 7.5 Hz, 2H), 7.50 (d, 8.5 Hz, 2H), 7.56 (d, 7.5 Hz, 2H); 13 C{ 1 H} NMR: (CDCl3) δ 24.34, 25.78, 50.82, 115.86, 116.81, 126.58, 126.68, 126.77, 128.37, 128.78.…”

New Monoorganostannanes as Efficient Reagents for Palladium-Catalyzed Coupling Reactions

“…Furthermore, this reaction appears to be totally regioselective for crotyl (Table , entry 4) or prenyl transfer (Table , entry 5), affording exclusively the transposed products 17 and 18 . The allenyl transfer is also achieved under particularly mild conditions (Table , entry 6), and double bond stereochemistry is totally preserved (Table , entries 9 and 10). Then, the use of a vinyl iodide as substrate allows a straightforward preparation of diene unit 23 .…”