Binap-silver salts as chiral catalysts for the enantioselective 1,3-dipolar cycloaddition of azomethine ylides and alkenes

Abstract

3 Stereochemistry AbstractTo create your abstract, type over the instructions in the template box below. Fonts or abstract dimensions should not be changed or altered. You may insert more abstracts by copying this box or by using the menu option to insert a stereochemistry abstract.J. Mancebo-Aracil , M. Martín-Rodríguez, C. Nájera, J. M. Sansano* , P. R. R. Costa, E. Crizanto de Lima, A. G Methyl (1S,3R,3aS,6aR)-5-methyl-3-phenyl-4,6-dioxooctahydro pyrrolo[3,4-c] Isopropyl (1S,3R,3aS,6aR)-5-methyl-3-phenyl-4,6-dioxoocta hydropyrrolo[3,4-c] Ethyl (1S,3R,3aS,6aR)-5-methyl-3-phenyl-4,6-dioxooctahydro pyrrolo[3,4-c] Methyl (1S,3R,3aS,6aR)-5-methyl-3-(2-naphthyl)-4,6-dioxoocta hydropyrrolo[3,4-c] tert- Butyl (1S,3R,3aS, Methyl (1S,3R,3aS,6aR)-5-methyl-4,6-dioxo-3-o-tolyloctahydropyrrolo[3,4-c] Methyl (1S,3R,3aS,6aR)-3-(2-chlorophenyl)-5-methyl-4,6-dioxooctahydropyrrolo[3,4-c] Methyl (1S,3R,3aS,6aR)-3-(3-pyridyl)-5-methyl-4,6-dioxooctahydropyrrolo[3,4-c] Methyl (1S,3R,3aS,6aR)-5-methyl-3-(4-methylphenyl)-4,6-dioxooctahydropyrrolo[3,4-c] Methyl (1S,3R,3aS,octahydropyrrolo [3,4-c] Methyl (1S,3R,3aS,6aR)-5-ethyl-4,6-dioxo-3-phenyloctahydropyrrolo[3,4-c] Methyl (1S,3R,3aS,6aR)-4,6-dioxo-3,5-diphenyloctahydropyrrolo[3,4-c] Methyl (1S,3R,3aS,6aR)-1,5-dimethyl-4,6-dioxo-3-phenyloctahydro pyrrolo[3,4-c] Methyl (1S,3R,3aS,6aR)-5-benzyl-4,6-dioxo-3-phenyloctahydropyrrolo[3,4-c] (1S,3R,3aS,6aR)-1 -isobutyl-5-methyl-4,6-dioxo-3-(2-thienyl)octahydropyrrolo [3,4-c] Methyl (1S,3R,3aS,6aR)-1-benzyl-5-methyl-4,6-dioxo-3-phenyl octahydropyrrolo[3,4-c] -indol-2-yl}-3,4-bis(phenylsulfonyl) Methyl (2R,3S,4S,5S)-5-[2-(2-acetoxyethyl)-4,5-dimethoxyphenyl]-3,4-bis(phenylsulfonyl) --- * Corresponding author. Tel.: +34-965903549; fax: +34-965903549; jmsansano@ua.es Methyl (1S,3R,3aS,6aR)-3-(4-chlorophenyl)-5-methyl-4,6-dioxooctahydropyrrolo[3,4-c]pyrrole-1-carboxylate Methyl (2R,3R,4R,5S)-5-(naphth-2-yl)-3,4-bis(phenylsulfonyl) pyrrolidine-2-carboxylate Methyl (2R,3R,4R,5S)-5-phenyl-3,4-bis(phenylsulfonyl)pyrrolidine-2-carboxylate Methyl (2R,3R,4R,5S)-3,4-bis(phenylsulfonyl)-5-(o-tolyl)pyrrolidine-2-carboxylate Methyl (2R,3R,4R,5S)-5-(4-methoxyphenyl)-3,4-bis(phenylsulfonyl)pyrrolidine-2-carboxylate Methyl (2R,3R,4R,5S)-3,4-bis(phenylsulfonyl)-5-(p-tolyl)pyrrolidine-2-carboxylate Isopropyl (2R,3R,4R,5S)-5-(4-chlorophenyl)-3,4-bis(phenylsulfonyl) pyrrolidine-2-carboxylate Methyl (2R,3R,4R,5S)-3,4-bis(phenylsulfonyl)-5-(pyrid-3-yl) pyrrolidine-2-carboxylate Methyl (2R,3R,4R,5S)-5-{3-[2-((tert-butyldimethylsilyl)oxy)ethyl]-1-(phenylsulfonyl)-1H A R T I C L E I N F O AB S T R AC TArticle history: Received Received in revised form Accepted Available onlineBinap-AgSbF6 catalyzed 1,3-dipolar cycloaddition between azomethine ylides and electrophilic alkenes is described an compared with the analogous transformations mediated by other Binapsilver(I) salt complexes. Maleimides and 1,2-bis(phenylsulfonyl)ethylene, are suitable dipolarophiles to obtain very good enantioselections, even better enantioselections are generated by the multicompone...

Coinage metal complexes as chiral catalysts for 1,3-dipolar cycloadditions

“…Cycloadduct endo-20 was obtained in good yields when both chiral catalysts were used, but the enantioselectivity achieved by (S a )-Binap-AgSbF 6 was noticeably higher. This was another evidence of the facility of the hexafluoroantimonate salt to perform cycloadditions with sterically hindered components [50].…”

“…However, analogous reactions carried out in the presence of (S)-Binap2·AgClO 4 complex failed. This was the first occasion that a three-component transformation is enantioselectively performed in the presence of a chiral Lewis acid [50].…”

“…Isomers 15 and 16were obtained after desulfonylation with 10% sodium amalgam in MeOH/THF and the crude mixture, without purification, was submitted to hydrogenation with Pt/C (10%). The enantiomeric excess of prolinate17 remained unaltered with respect to the starting disulfonylatedheterocycle14a, being 47% the overall yield of 17 (Scheme 7) [50].…”

“…Besides, the catalytic complex could not be recovered and reused in additional catalytic processes. An interesting alternative solution to these problems was found in parallel studies carried out with another privileged ligand such as chiral binap 2 [47,48,49,50].…”

Asymmetric 1,3-Dipolar Cycloadditons of Stabilized Azomethine Ylides with Nitroalkenes

“…A large series of dipolarophiles have been successfully tested demonstrating the wide scope (higher than the analogous for the chiral copper-catalyzed cycloadditions) exhibited by the employment of this cation [60][61][62][63][64][65][66][67][68][69][70]. Despite the versatility shown by these metal the employment of nitroalkenes 10 was very scarce.…”