Journal of the American Chemical Society, Год журнала: 2025, Номер unknown
Опубликована: Апрель 30, 2025
Transition metal-catalyzed higher-order cycloadditions involving vinylcyclopropenes (VCPEs) have not been realized to synthesize challenging medium-sized rings, partially due their poor stability and many competing side reactions. We report here a Rh-catalyzed [5 + 1 2] reaction of yne-VCPEs CO for the synthesis eight-membered carbocycles with trienone moiety, which so far can be accessed by only limited The key this cycloaddition is that once C-C cleavage VCPE (C5 synthon) form six-membered metallacycle initiated, (C1 insertion happens before alkyne (C2 insertion, attributing special reactivity sp2 carbon in vinylcyclopropene. Quantum chemical calculations applied support pathway. present has broad scope, C2 synthon also extended alkenes allene. Of same importance, catalyzed either [Rh(CO)2Cl]2 or cheaper complex, RhCl3·nH2O.
Язык: Английский