Pd(II)-Catalyzed Atroposelective C−H Olefination to Access [n]Naphthalenophanes

Abstract

A Pd-catalyzed late-stage C–H olefination of [n]naphthalenophanes has been developed. This method enables the synthesis of a series of enantiomerically enriched [n]naphthalenophanes with high chemoselectivity. The origin of atropisomerism was investigated through thermal stability studies and reductive cleavage experiments. Moreover, a bifunctional thiourea organocatalyst derived from naphthalenophanes demonstrates promising potential in promoting Michael addition reactions, underscoring the versatility of cyclophanes in asymmetric synthesis. The synthesized [14]naphthalenophane 10 exhibited a dissymmetry factor (|glum|) of 1.0 × 10⁻³ and an absolute fluorescence quantum yield of 20.2%.