Mild and stereoselective synthesis of (1E,3E)-dienes through silver(I)-catalyzed β-hydride migration from allylic α-diazo esters

Abstract

A mild procedure for the diastereoselective preparation of functionalized 1,3-dienes and their synthetic versatility are described herein. The silver-catalyzed decomposition of α-diazo-γ,δ-unsaturated esters through β-hydride migration at room temperature resulted in the stereoselective formation of 12 conjugated (1E,3E)-dienes. Further synthetic post-modifications included intramolecular Heck reaction and hydrogenation, leading to a novel substituted indene and an aliphatic diester, respectively. To rationalize the observed reaction outcome, a computational investigation of the mechanisms was conducted, emphasizing the importance of factors such as metallocarbenoid stability, substituent effects, and microkinetics simulations to better understand the reaction intricacies.