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Article Abstract
A stereodivergent synthesis of bicyclic α--, β--, and α--glycosides is achieved with nonprecious Co(dpm), KCO, and DBU, respectively. Cobalt-catalyzed decarboxylative allylation of 2,3-unsaturated 4-keto glycosyl carbonates with 1,3-diketones delivers α--glycosides in good yields with exclusive chemo- and regiocontrol and excellent diastereoselectivity (>20:1 dr). KCO enables β--glycosides via a cascaded intermolecular Michael addition/S2-like cyclization, whereas DBU promotes further C5 epimerization to give α--glycosides. Mechanistic studies (deuterium labeling and intermediate capturing) validate the pathways. Gram-scale synthesis and late-stage functionalization of pharmaceuticals demonstrate practicality.
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| http://dx.doi.org/10.1021/acs.orglett.5c01433 | DOI Listing |
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