Charge Relocation Enables a Modular and Diastereoselective Synthesis of <i>cis</i> ‐Substituted Tetrahydrofurans

Diastereoselective construction of organic scaffolds from simple and commercial materials is a powerful strategy in contemporary organic synthesis. Herein, we report a novel disconnection for the direct preparation of tetrahydrofurans (THFs) and corresponding derivatives from acyl chlorides and alkenes using charge relocation. Newly synthesised Hantzsch ester derivatives, functioning both as hydride sources and selectivity modulators, enabled exceptional diastereoselectivity. The wide range of alkenes tolerated is a highlight of the method, enabling the construction of structurally distinct THF-containing skeletons.