A Stereoconvergent Tsuji–Trost Reaction in the Synthesis of Cyclohexenyl Nucleosides. Issue 12 (11th February 2020)

• Record Type: Journal Article
• Authors: Esposito, Anna; di Giovanni, Concetta; De Fenza, Maria; Talarico, Giovanni; Chino, Marco; Palumbo, Giovanni; Guaragna, Annalisa; D'Alonzo, Daniele
• Is Part Of: Chemistry. Volume 26:Issue 12(2020)
• Page Start: 2597
• Page End: 2601
• Publication Date: 2020-02-11
• Subjects: antiviral agents -- carbocyclic nucleosides -- density functional calculations -- stereoconvergent reaction -- Tsuji–Trost reaction; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201905367
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: A highly regio‐ and stereoselective route to d ‐ and l ‐cyclohexenyl nucleosides has been devised, using the Tsuji–Trost reaction as the key step. Contrarily to the widely accepted mechanism (involving a net retention of configuration), the reaction proceeded in a highly stereoconvergent manner, providing cis nucleosides regardless of the relative configuration of the starting materials. DFT calculations confirmed the experimental data while suggesting the origin of the stereochemical reaction outcome. Abstract : All roads lead to cis : contrarily to its well‐established reaction mechanism, the Tsuji–Trost reaction of cyclohexene‐based substrates proceeds under highly stereoconvergent conditions, leading to cis ‐nucleosides regardless of the relative configuration of the starting materials. Experimental data and DFT calculations enabled to shed light on the origin of the unprecedented stereochemical outcome of the reaction.