Carbohydrates are abundant renewable resources and are a feedstock for green chemistry and sustainable synthesis of the future. Among the hexoses and the pentoses present in biomass, mannitol was selected in the present project as a valuable platform, directly available from the chiral pool, to build highly functionalized molecules. Starting from (R)-2,3-O-cyclohexylidene glyceraldehyde, which is easily prepared in a large scale from D-mannitol, an enantiopure chiral nitro alkene was prepared by reaction with nitromethane, and its reactivity studied. Organocatalytic Michael addition of dimethyl malonate, β-keto esters, and other nucleophiles on the nitro alkene afforded high stereoselectivity and densely functionalized chiral molecules, which were further synthetically developed, leading to five-membered lactones and bicyclic lactams. Preliminary studies showed that the metal-free catalytic reaction on the chiral nitro alkene can be performed under continuous flow conditions, thus enabling the use of (micro)mesofluidic systems for the preparation of enantiomerically pure organic molecules from the chiral pool.

Organocatalytic Michael addition to (D)-mannitol-derived enantiopure nitroalkenes: A valuable strategy for the synthesis of densely functionalized chiral molecules / L. Caruso, A. Puglisi, E. Gillon, M. Benaglia. - In: MOLECULES. - ISSN 1420-3049. - 24:24(2019 Dec 14), pp. 4588.1-4588.10. [10.3390/molecules24244588]

Organocatalytic Michael addition to (D)-mannitol-derived enantiopure nitroalkenes: A valuable strategy for the synthesis of densely functionalized chiral molecules

L. Caruso
Primo
;
A. Puglisi
Secondo
;
M. Benaglia
Ultimo
2019

Abstract

Carbohydrates are abundant renewable resources and are a feedstock for green chemistry and sustainable synthesis of the future. Among the hexoses and the pentoses present in biomass, mannitol was selected in the present project as a valuable platform, directly available from the chiral pool, to build highly functionalized molecules. Starting from (R)-2,3-O-cyclohexylidene glyceraldehyde, which is easily prepared in a large scale from D-mannitol, an enantiopure chiral nitro alkene was prepared by reaction with nitromethane, and its reactivity studied. Organocatalytic Michael addition of dimethyl malonate, β-keto esters, and other nucleophiles on the nitro alkene afforded high stereoselectivity and densely functionalized chiral molecules, which were further synthetically developed, leading to five-membered lactones and bicyclic lactams. Preliminary studies showed that the metal-free catalytic reaction on the chiral nitro alkene can be performed under continuous flow conditions, thus enabling the use of (micro)mesofluidic systems for the preparation of enantiomerically pure organic molecules from the chiral pool.
nitro alkenes; stereoselective synthesis; renewable sources; organocatalysis; chiral molecules;
Settore CHIM/06 - Chimica Organica
Enabling TECHNOlogies-driven chemistry: a tailored TRAINing research program for batch and flow synthesis of chiral amino derivatives (TECHNOTRAIN)
PIANO DI SOSTEGNO ALLA RICERCA 2015-2017 - TRANSITION GRANT LINEA 1A PROGETTO "UNIMI PARTENARIATI H2020"
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/707982
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