López-Francés Adrián, Serna-Burgos Zuriñe, Del Corte Xabier, de Los Santos Jesús M, de Cózar Abel, Vicario Javier
Department of Organic Chemistry I, Faculty of Pharmacy, University of the Basque Country, UPV/EHU. Paseo de la Universidad 7, Vitoria-Gasteiz 01006, Spain.
Department of Organic Chemistry I, Donostia International Physics Centre (DIPC), University of the Basque Country, UPV/EHU. Paseo Manuel de Lardizabal, 3, Donostia-San Sebastián 20018, Spain.
J Org Chem. 2024 Jul 5;89(13):9502-9515. doi: 10.1021/acs.joc.4c00822. Epub 2024 Jun 19.
A study on the reactivity of rigid 1-azadienes derived from methylene γ-lactams is reported. Through the functionalization of 1-amino α,β-unsaturated γ-lactam derivatives, easily available from a multicomponent reaction of amines, aldehydes, and pyruvates, it is possible to in situ generate rigid 1-azadienes locked by a γ-lactam core. The 4π-electron system of those rigid 1-azadienes can behave as both diene and dienophile species through a spontaneous cyclodimerization reaction or exclusively as dienes or dienophiles if they are trapped with imines or cyclopentadiene, respectively. The use of chiral rigid 1-azadienes as dienophiles in the cycloaddition reaction with cyclopentadiene leads to the formation of spiro-γ-lactams bearing four stereogenic centers in a highly stereospecific manner, reporting the first example of the use of methylene-γ-lactams in the synthesis of spirocycles.
本文报道了一项关于源自亚甲基γ-内酰胺的刚性1-氮杂二烯反应活性的研究。通过对1-氨基α,β-不饱和γ-内酰胺衍生物进行官能化反应（该衍生物可通过胺、醛和丙酮酸的多组分反应轻松制得），能够原位生成由γ-内酰胺核心锁定的刚性1-氮杂二烯。这些刚性1-氮杂二烯的4π电子体系可通过自发的环二聚反应同时表现出双烯和亲双烯体的性质，或者如果分别用亚胺或环戊二烯捕获，则仅表现为双烯或亲双烯体。在手性刚性1-氮杂二烯作为亲双烯体与环戊二烯进行环加成反应时，会以高度立体专一的方式形成带有四个立体中心的螺环γ-内酰胺，这是亚甲基γ-内酰胺用于螺环合成的首个实例报道。
