Synthesis of (−)‐8a‐epi‐Lentiginosine via Tsuji–Trost Reaction of d ‐Glucose‐Derived Allylic Alcohols and Crystal Structure Analysis
Year: 2025
Type: article
Abstract: An indolizidine alkaloid, (−)‐8a‐epi‐lentiginosine was synthesized from d‐glucose using the Pd‐BiPhePhos catalyzed intramolecular Tsuji–Trost reaction of non−derivatized allylic alcohol as a key construction of the hydroxylated pyrrolidine ring to give the desired product in good yield and high stereospecificity (dr = 97:3). The absolute configuration and structure of (−)‐8a‐epi‐lentiginosine were confirmed by NMR and X‐ray crystal structure analysis. The crystal structure of (−)‐8a‐epi‐lentiginosne showed the envelope conformation of the five‐membered ring, which is an N‐atom in the endo‐position, and the fused six‐membered ring adopts a chair conformation similar to the DFT optimized structure. The solid‐state packing is dominated by a 1D‐hydrogen‐bonded network along the a‐axis involving both hydroxyl groups and the amine. The large HOMO–LUMO energy gap indicated the high stability of the compound.
Institutions: Kasetsart University, Uppsala University, Stockholm University
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,030
Funder: Vetenskapsrådet
OpenAlex ID: W4409786898