Asymmetric Olefin Isomerization via Phase-Transfer-Catalyzed [1,3]-Hydrogen Transfer for Access to Axially Chiral Furan-Benzimidazoles

作者：Yu‐Qing Guan, Kaili Ma, Dong‐Chao Wang, Hai‐Ming Guo · 发表于：Organic Letters · 年份：2025 · DOI：10.1021/acs.orglett.5c01181 · 被引用次数：8 · 研究领域：Axial and Atropisomeric Chirality Synthesis、Molecular spectroscopy and chirality、Sphingolipid Metabolism and Signaling

An efficient catalytic asymmetric olefin isomerization of axially chiral methylene dihydrofuran-benzimidazoles via kinetic resolution is reported. Under mild phase-transfer catalysis, axially chiral furan-benzimidazole compounds and recovered methylene dihydrofuran-benzimidazoles were obtained in high ee. The combination of the kinetic resolution and TBD-catalyzed isomerization of recovered dihydrofuran-benzimidazoles provided access to both enantiomers of furan-benzimidazoles. Deuterium-labeling experiments reveal intramolecular [1,3]-H transfer mechanism. The utility of this method was demonstrated by scale-up synthesis and functionalization of the products.