Bismuth- and hafnium-catalyzed hydroamination of vinyl arenes with sulfonamides, carbamates, and carboxamides.
Catalytic intermolecular hydroamination of vinyl arenes is described. Our initial investigation revealed that a Bi(OTf)3/[Cu(CH3CN)4]PF6 system previously developed for catalytic intermolecular hydroamination of 1,3-dienes was suitable for hydroamination of a styrene with sulfonamides, but the substrate generality of this system was unsatisfactory. Several metals were screened to expand the substrate scope, and a new Hf(OTf)4/[Cu(CH3CN)4]PF6 system was determined to be highly suitable. The combination of Hf(OTf)4 and [Cu(CH3CN)4]PF6 efficiently promoted the hydroamination of various vinyl arenes, including less-reactive vinyl arenes with electron-withdrawing groups. This strategy was applied to sulfonamides, carbamates, and carboxamides, and products were obtained in up to 99% yield with 0.3-10 mol % catalyst loading.
Qin
Hongbo
H
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Yamagiwa
Noriyuki
N
Matsunaga
Shigeki
S
Shibasaki
Masakatsu
M
D000577:Amides / Q000737:chemistry; D000586:Amination; D001729:Bismuth / Q000737:chemistry*; D002219:Carbamates / Q000737:chemistry*; D002384:Catalysis; D006195:Hafnium / Q000737:chemistry*; D006841:Hydrocarbons, Aromatic / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D013449:Sulfonamides / Q000737:chemistry*; D014753:Vinyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry
D000577:Amides; D002219:Carbamates; D006841:Hydrocarbons, Aromatic; D013449:Sulfonamides; D014753:Vinyl Compounds; D001729:Bismuth; D006195:Hafnium