由N-铼胺合成β-内酰胺：过渡金属对施陶丁格反应能量分布的影响
Synthesis of beta-lactams from a N-rhenaimine: effect of the transition metal on the energetic profile of the Staudinger reaction.
作者信息
Hevia Eva, Pérez Julio, Riera Víctor, Miguel Daniel, Campomanes Pablo, Menéndez M Isabel, Sordo Tomás L, García-Granda Santiago
机构信息
Departamentos de Química Orgánica e Inorgánica-IUQOEM y de Química Física y Analítica, Universidad de Oviedo, Spain.
出版信息
J Am Chem Soc. 2003 Apr 2;125(13):3706-7. doi: 10.1021/ja034070s.
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.
如图所示，亚烷基氨基络合物1（一种N-铼亚胺）与烯酮反应生成β-内酰胺2-4，这些β-内酰胺在氮原子处具有{Re(CO)3(bpy)}片段作为取代基。使用HOTf或MeOTf进行的完全脱金属反应生成游离的β-内酰胺或N-甲基-β-内酰胺以及[Re(OTf)(CO)3(bpy)]。密度泛函理论计算有助于解释该反应为何比非过渡金属N-取代亚胺的反应更快。
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