title: Synthesis of Enantiopure 1,2-Diaminobicyclo[2.2.2]octane Derivatives, C1-Symmetric Chiral 1,2-Diamines with a Rigid Bicyclic Backbone.
abstract: The synthesis of enantiopure 1,2-diaminobicyclo[2.2.2]octane (DABO, 1) and its two selectively N-Boc monoprotected derivatives 15 and 16 is described. Starting from bicyclic β-amino acid 3 or 5, strategies involving Curtius and Hofmann rearrangements were explored, demonstrating the unprecedented influence of the bicyclic backbone unsaturation for the preparation of the corresponding diamines that could be only obtained in good yield using the Hofmann rearrangement of unsaturated compound 3. The divergent outcome observed during the Hofmann rearrangement of 3 and 5 was investigated by DFT calculations.
authors.affiliation: IBMM, UMR-5247, CNRS, Université Montpellier , ENSCM, Place E. Bataillon, 34095 Montpellier Cedex 5, France.
authors.forename: Pierre
authors.initials: P
authors.lastname: Milbeo
authors.affiliation: IBMM, UMR-5247, CNRS, Université Montpellier , ENSCM, Place E. Bataillon, 34095 Montpellier Cedex 5, France.
authors.forename: Laure
authors.initials: L
authors.lastname: Moulat
authors.affiliation: CRM2, UMR 7036, CNRS, Université de Lorraine , Boulevard des Aiguillettes, 54506 Vandoeuvre-lès-Nancy, France.
authors.forename: Claude
authors.initials: C
authors.lastname: Didierjean
authors.affiliation: CRM2, UMR 7036, CNRS, Université de Lorraine , Boulevard des Aiguillettes, 54506 Vandoeuvre-lès-Nancy, France.
authors.forename: Emmanuel
authors.initials: E
authors.lastname: Aubert
authors.affiliation: IBMM, UMR-5247, CNRS, Université Montpellier , ENSCM, Place E. Bataillon, 34095 Montpellier Cedex 5, France.
authors.forename: Jean
authors.initials: J
authors.lastname: Martinez
authors.affiliation: IBMM, UMR-5247, CNRS, Université Montpellier , ENSCM, Place E. Bataillon, 34095 Montpellier Cedex 5, France.
authors.forename: Monique
authors.identifier: 0000-0001-7690-0206
authors.initials: M
authors.lastname: Calmès