Journal Article Highly Selective Carboxylative Cyclization of Allenylmethylamines with Carbon Dioxide Using N-heterocyclic Carbene–Silver Catalysts

山下, 恭平  ,  Yamashita, Kyouhei  ,  長谷, 俊  ,  Hase, Shun  ,  榧木, 啓人  ,  Kayaki, Yoshihito  ,  碇屋, 隆雄  ,  IKARIYA, TAKAO

17 ( No. 10 )  , pp.2334 - 2337 , 2015-04 , American Chemical Society
Silver(I) carboxylate complexes promote the carboxylative cyclization of allenylmethylamines to afford 5-alkenyl-1,3-oxazolidin-2-ones in 2-propanol. The use of an N-heterocyclic carbene ligand (IPr) under pressurized CO2 is effective in suppressing the intramolecular hydroamination that leads to 2,5-dihydropyrroles. The mechanism involving a nucleophilic attack of the carbamate of the allene moiety and a subsequent protonation was realized on the basis of experimental and theoretical results involving a model intermediate, the alkenylgold(I) complex, which was synthesized from Au(OH)(IPr) and 1-methylamino-2,3-butadiene.

Number of accesses :  

Other information