Asymmetric Transfer Hydrogenation of Acyclic 1,4-Diketones for the Synthesis of Diversified Cyclic Products via Double Dynamic Kinetic Resolution

In this full article, we report on the selective ATH of acyclic racemic 1,4-diketones. By modulating the electron-withdrawing groups (EWGs) on the substrates and tuning the reaction conditions, four types of cyclic productsincluding dihydrofurans, γ-lactones, tetrahydrofuranols, and tetrahydrofuransare obtained through a double dynamic kinetic resolution (DKR) process.

Moreover, the synthetic value of this method has been demonstrated by the synthesis of five bioactive compounds, i.e., megacerotonic acid, (7′<i>E</i>)-(7<i>R</i>,8<i>R</i>)-salvianolic acid V, prunellanate B, calyxolane A, and a magnosalicin-type neolignane, which fall into three categories of active molecular families. Mechanistic insights are further elucidated through combined experimental studies and density functional theory (DFT) calculations.