Chiral heteropolycyclic structures are widespread in compounds of high pharmaceutical relevance. In particular, linear fused pyran-dioxane based polycycles can be found in several naturally occurring molecules, and among them, cardiac glycosides and antibiotic spectinomycin are characterized by a cis-cisoid-trans geometry. Then, the stereocontrol in the synthesis of this type of polycyclic scaffold is of primary importance. Herein, we present two novel linear fused pyran-dioxane based bi- and tricycles, synthesized with total stereoselectivity from a glycal derived vinyl epoxide. The straightforward methodology described involves a substrate-dependent stereospecific glycosylation step followed by an intramolecular S(N)2 ' conjugate addition process, leading to a pyran-dioxane-cyclohexane tricycle with a cis-cisoid-trans stereochemistry, in agreement with the geometry of many natural products. The stereochemical analysis of these compounds, which was realized by a combined NMR/computational approach, is also reported.

Stereoselective synthesis of new pyran-dioxane based polycycles from glycal derived vinyl epoxide

Iacopini, Dalila
Primo
;
Favero, Lucilla;Pineschi, Mauro;Di Pietro, Sebastiano
Penultimo
;
Di Bussolo, Valeria
Ultimo
2021-01-01

Abstract

Chiral heteropolycyclic structures are widespread in compounds of high pharmaceutical relevance. In particular, linear fused pyran-dioxane based polycycles can be found in several naturally occurring molecules, and among them, cardiac glycosides and antibiotic spectinomycin are characterized by a cis-cisoid-trans geometry. Then, the stereocontrol in the synthesis of this type of polycyclic scaffold is of primary importance. Herein, we present two novel linear fused pyran-dioxane based bi- and tricycles, synthesized with total stereoselectivity from a glycal derived vinyl epoxide. The straightforward methodology described involves a substrate-dependent stereospecific glycosylation step followed by an intramolecular S(N)2 ' conjugate addition process, leading to a pyran-dioxane-cyclohexane tricycle with a cis-cisoid-trans stereochemistry, in agreement with the geometry of many natural products. The stereochemical analysis of these compounds, which was realized by a combined NMR/computational approach, is also reported.
2021
Iacopini, Dalila; Barbini, Gabriele; Favero, Lucilla; Pineschi, Mauro; Di Pietro, Sebastiano; Di Bussolo, Valeria
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11568/1110426
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