Three-component modular synthesis of chiral 1,3-dioxoles a Rh-catalyzed carbenic olefination cascade.

The advance of organic synthesis and the discovery of novel chemical transformations are often propelled by the rational programming of various bond-forming mechanisms and sequences that involve delicate reactive intermediates. In this study, we present an innovative Rh(ii)-catalyzed asymmetric three-component cascade reaction involving I/P-hybrid ylides, aldehydes, and carboxylic acids for the synthesis of 1,3-dioxoles with moderate to good yields and high enantioselectivity. This method utilizes I/P-hybrid ylides as carbene precursors to form α-P-Rh-carbenes, which initiate the formation of carbonyl ylides, followed by stereoselective cyclization with carboxylate anions and an intramolecular Wittig olefination cascade, ultimately resulting in the modular assembly of chiral 1,3-dioxoles. By employing this strategy, we successfully coupled various aldehydes and carboxylic acids to give chiral non-benzofused 1,3-dioxole scaffolds, highlighting the potential for late-stage functionalization of biologically relevant molecules, versatile synthetic manipulation, and the production of poly-1,3-dioxole macromolecules.