Qin Hongbo, Yamagiwa Noriyuki, Matsunaga Shigeki, Shibasaki Masakatsu
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
J Am Chem Soc. 2006 Feb 8;128(5):1611-4. doi: 10.1021/ja056112d.
A Bi(OTf)(3)/Cu(CH(3)CN)(4)PF(6) system efficiently promoted intermolecular 1:1 hydroamination of 1,3-dienes with various carbamates, sulfonamides, and carboxamides to afford allylic amines in good yield (up to 96%). Reaction proceeded with 0.5-10 mol % catalyst loading at 25-100 degrees C (generally at 50 degrees C) in 1,4-dioxane within 24 h. The Bi(OTf)(3)/Cu(CH(3)CN)(4)PF(6) system constitutes a new entry into series of intermolecular hydroamination catalysis. Mechanistic studies and the postulated reaction mechanism are also discussed.
Bi(OTf)₃/Cu(CH₃CN)₄PF₆体系能有效促进1,3 - 二烯与各种氨基甲酸酯、磺酰胺和羧酰胺的分子间1:1氢胺化反应，以良好的产率（高达96%）得到烯丙基胺。反应在25 - 100℃（通常为50℃）下，于1,4 - 二氧六环中，催化剂负载量为0.5 - 10 mol%时，24小时内即可进行。Bi(OTf)₃/Cu(CH₃CN)₄PF₆体系为分子间氢胺化催化系列提供了新的方法。还讨论了机理研究和推测的反应机理。
