DNA‐Based Asymmetric Inverse Electron‐Demand Hetero‐Diels–Alder
Justine Mansot, Jimmy Lauberteaux, Aurélien Lebrun, Marc Mauduit, Jean‐Jacques Vasseur, Renata Marcia de Figueiredo, Stellios Arseniyadis, Jean‐Marc Campagne, Michaël Smietana
Abstract
While artificial cyclases hold great promise in chemical synthesis, this work presents the first example of a DNA-catalyzed inverse electron-demand hetero-Diels-Alder (IEDHDA) between dihydrofuran and various α,β-unsaturated acyl imidazoles. The resulting fused bicyclic O,O-acetals containing three contiguous stereogenic centers are obtained in high yields (up to 99 %) and excellent diastereo- (up to >99:1 dr) and enantioselectivities (up to 95 % ee) using a low catalyst loading. Most importantly, these results show that the concept of DNA-based asymmetric catalysis can be expanded to new synthetic transformations offering an efficient, sustainable, and highly selective tool for the construction of chiral building blocks.