A metal-free, mild and chemodivergent transformation involving nitroalkanes has been developed. Under optimized reaction conditions, in the presence of trichlorosilane and a tertiary amine, aliphatic nitroalkanes were selectively converted into amines or nitriles. Furthermore, when chiral β-substituted nitro compounds were reacted, the stereochemical integrity of the stereocenter was maintained and α-functionalized nitriles were obtained with no loss of enantiomeric excess. The methodology was successfully applied to the synthesis of chiral β-cyano esters, α-aryl alkylnitriles, and TBS-protected cyanohydrins, including direct precursors of four active pharmaceutical ingredients (ibuprofen, tembamide, aegeline and denopamine).

Metal-Free Deoxygenation of Chiral Nitroalkanes : An Easy Entry to α-Substituted Enantiomerically Enriched Nitriles / M. Pirola, C. Faverio, M. Orlandi, M. Benaglia. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - 27:40(2021), pp. 10247-10250. [10.1002/chem.202100889]

Metal-Free Deoxygenation of Chiral Nitroalkanes : An Easy Entry to α-Substituted Enantiomerically Enriched Nitriles

M. Pirola;C. Faverio;M. Benaglia
2021

Abstract

A metal-free, mild and chemodivergent transformation involving nitroalkanes has been developed. Under optimized reaction conditions, in the presence of trichlorosilane and a tertiary amine, aliphatic nitroalkanes were selectively converted into amines or nitriles. Furthermore, when chiral β-substituted nitro compounds were reacted, the stereochemical integrity of the stereocenter was maintained and α-functionalized nitriles were obtained with no loss of enantiomeric excess. The methodology was successfully applied to the synthesis of chiral β-cyano esters, α-aryl alkylnitriles, and TBS-protected cyanohydrins, including direct precursors of four active pharmaceutical ingredients (ibuprofen, tembamide, aegeline and denopamine).
chiral nitriles, metal-free reactions; nitroalkanes; stereoselectivity; trichlorosilane
Settore CHIM/06 - Chimica Organica
PRIN201719MBENA_01 - Unlocking Sustainable Technologies Through Nature-Inspired Solvents (NATUREChem) - BENAGLIA, MAURIZIO - PRIN2017 - PRIN bando 2017 - 2019
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/871162
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