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revised on 15.10.2019, 17:53 and posted on 16.10.2019, 07:37by Carlos Palo-Nieto, Abhijit Sau, Robin Jeanneret, Pierre-Adrien Payard, Maristela Braga Martins-Teixeira, Ivone Carvalho, Laurence Grimaud, M. Carmen Galan
We demonstrate that tuning the reactivity of Cu by the choice of oxidation state and counterion leads to the activation of both “armed” and “disarmed” type glycals towards direct glycosylation leading to the a-stereoselective synthesis of deoxyglycosides in good to excellent yields. Mechanistic studies show that CuI is essential for effective catalysis and stereocontrol and that the reaction proceeds through dual activation of both the enol ether as well as the OH nucleophile.
MCG, RJ and AS thank the European Research Council (ERCCOG: 648239) and CPN thanks RS Newton Fellowship. LG thanks the CNRS, the ENS/PSL and the ENS Paris Saclay (Ph.D. scholarship to P.-A.P.) for financial support. IC and MBMT thank Fundação de Amparo à Pesquisa do Estado de São Paulo - FAPESP Proc n. 2016/21194-6