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Palladium-catalyzed allylic substitution between C-based nucleophiles and 6-azabicyclo[3.1.0]-hex-3-en-2-oxy derivatives: A new selectivity paradigm

Abstract : The reaction between a-hydroxy-(or a-acetoxy) cyclopenten-aziridines (6-azabicyclo[3.1.0]hex-3-en-2ols or acetates) and C-based nucleophiles in the presence of Pd(0)-catalysis was investigated. In all the cases studied, the reaction was totally regio-and diastereo-selective, affording a single adduct in moderate to good yields. Specifically, attack of the nucleophile at position 3 of the cyclopentene moiety, anti to the vicinal oxy group, with vinylogous ring opening of the aziridine ring, was observed. When the carbon acid is a very acidic methylene (pK a (DMSO) 7.3), the resulting adduct is a zwitterion, resulting from an intramolecular proton transfer between the amino group and the carbon acid moiety taking place after the CeC bond formation. A plausible mechanism for this transformation is put forward.
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Submitted on : Tuesday, February 23, 2021 - 11:43:44 AM
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João A.C. Oliveira, Aurélie Bernard, Joao Oliveira, Gredy Kiala, Filipa Siopa, et al.. Palladium-catalyzed allylic substitution between C-based nucleophiles and 6-azabicyclo[3.1.0]-hex-3-en-2-oxy derivatives: A new selectivity paradigm. Tetrahedron, Elsevier, 2020, 76 (51), pp.131182. ⟨10.1016/j.tet.2020.131182⟩. ⟨hal-03148563⟩

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