Year: 2025
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide An efficient and mild Cu(I)-catalyzed Michael-type conjugate addition for 2-nitro glycals to access O-, S-, and C -glycosides with high stereoselectivity is reported. Under optimized conditions, nitrogalactals achieved high α-selectivity, whereas nitroglucal predominantly gave β-selective glycosides. The method is further demonstrated with other Michael-type substrates, including 2-formyl glycals and 3-keto glycals. Initial mechanistic investigations using NMR and supported by DFT calculations suggest that the reaction proceeds via a preorganized complex that positions the nucleophile close to the double bond to promote the Michael-type addition, in a manner analogous to enzyme-catalyzed processes. Moreover, the versatility of this synthetic approach was exemplified in the stereoselective synthesis of a mucin-type glycopeptide and the chemoselective one-pot synthesis of a trisaccharide.
Source: The Journal of Organic Chemistry
Authors: Mukul Mahanti, Carla M. Saunders, Nicholas Walker, Natalie Fey, M. Carmen Galan
Institution: University of Bristol
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
OpenAlex ID: W4410528610