Synthesis of beta-lactams from a N-rhenaimine: effect of the transition metal on the energetic profile of the Staudinger reaction.
As depicted in the scheme, the alkylidenamido complex 1, a N-rhenaimine, reacts with ketenes to afford the beta-lactams 2-4, which possess a {Re(CO)3(bpy)} fragment as substituent at nitrogen. Clean demetalations using HOTf or MeOTf yield the free beta-lactams or N-methyl-beta-lactams along with [Re(OTf)(CO)3(bpy)]. DFT calculations help to rationalize why the reaction is faster than those of non transition metal N-substituted imines.
Hevia
Eva
E
Departamentos de Química Orgánica e Inorgánica-IUQOEM y de Química Física y Analítica, Universidad de Oviedo, Spain.
Pérez
Julio
J
Riera
Víctor
V
Miguel
Daniel
D
Campomanes
Pablo
P
Menéndez
M Isabel
MI
Sordo
Tomás L
TL
García-Granda
Santiago
S
D000900:Anti-Bacterial Agents / Q000138:chemical synthesis / Q000737:chemistry; D003500:Cyclization; D005030:Ethylenes / Q000737:chemistry; D007659:Ketones / Q000737:chemistry; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000737:chemistry*; D012211:Rhenium / Q000737:chemistry*; D013816:Thermodynamics; D047090:beta-Lactams / Q000138:chemical synthesis* / Q000737:chemistry
D000900:Anti-Bacterial Agents; D005030:Ethylenes; D007659:Ketones; D009942:Organometallic Compounds; D047090:beta-Lactams; D012211:Rhenium; C008223:ketene