Cobalt-Catalyzed versus Base-Promoted Skeletal- and Stereodivergent Synthesis of Bicyclic α-<i>C</i>-, β-<i>O</i>-, and α-<i>O</i>-Glycosides
A stereodivergent synthesis of bicyclic α-<i>C</i>-, β-<i>O</i>-, and α-<i>O</i>-glycosides is achieved with nonprecious Co(dpm)<sub>3</sub>, K<sub>2</sub>CO<sub>3</sub>, and DBU, respectively. Cobalt-catalyzed decarboxylative allylation of 2,3-unsaturated 4-keto glycosyl carbonates with 1,3-diketones delivers α-<i>C</i>-glycosides in good yields with exclusive chemo- and regiocontrol and excellent diastereoselectivity (>20:1 dr). K<sub>2</sub>CO<sub>3</sub> enables β-<i>O</i>-glycosides via a cascaded intermolecular Michael addition/S<sub>N</sub>2-like cyclization, whereas DBU promotes further C5 epimerization to give α-<i>O</i>-glycosides. Mechanistic studies (deuterium labeling and intermediate capturing) validate the pathways. Gram-scale synthesis and late-stage functionalization of pharmaceuticals demonstrate practicality.
Authors
- Xingxing Jiang (ORCID: https://orcid.org/0000-0001-6068-8773)
- Nengzhong Wang (ORCID: https://orcid.org/0000-0003-1690-7611)
- Zhen Cao (ORCID: https://orcid.org/0000-0003-3369-5526)
- Yujie Niu (ORCID: https://orcid.org/0000-0002-0912-8401)
- Hui Qin Yao (ORCID: https://orcid.org/0000-0002-4450-8602)
- Nianyu Huang (ORCID: https://orcid.org/0000-0003-4483-160X)
- Linxuan Li (ORCID: https://orcid.org/0000-0001-9836-1442)
Institutions
- China Three Gorges University (CN)
Publication Details
- Journal
- Organic Letters
- Published
- 2025-05-09
- DOI
- https://doi.org/10.1021/acs.orglett.5c01433
- Citations
- 3
- Primary Topic
- Carbohydrate Chemistry and Synthesis
- Type
- article
- Field-Weighted Citation Impact
- 2.81
Funders
- National Natural Science Foundation of China
- Natural Science Foundation of Hubei Province
- Higher Education Discipline Innovation Project
- Hubei Provincial Central Guidance Local Science and Technology Development Project