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. 2019 Feb 8:7:62.
doi: 10.3389/fchem.2019.00062. eCollection 2019.

Synthesis of Oxazinanones: Intramolecular Cyclization of Amino Acid-Derived Diazoketones via Silica-Supported HClO4 Catalysis

Rafael D C Gallo  1 , Orlando C Campovilla Jr  1 , Anees Ahmad  1 , Antonio C B Burtoloso  1
Affiliations

Synthesis of Oxazinanones: Intramolecular Cyclization of Amino Acid-Derived Diazoketones via Silica-Supported HClO4 Catalysis

Rafael D C Gallo et al. Front Chem. .

Abstract

A Brønsted acid catalyzed intramolecular cyclization of N-Cbz-protected diazoketones, derived from α-amino acids, is described. The reaction proceeds under metal-free conditions and is promoted by ecofriendly silica-supported HClO4 as the catalyst and methanol as the solvent. This transformation enables the short synthesis of various 1,3-oxazinane-2,5-diones under mild reaction conditions and in good yields (up to 90%). The set-up is very simple; by just mixing all reagents together with no work-up necessary before purification, this protocol takes a greener approach.

Keywords: Brønsted acid; diazo carbonyls; heterocycles; intramolecular cyclization; oxazinanones.

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Figures

Figure 1
Figure 1
Bioactive molecules bearing an oxazinanone moiety.
Figure 2
Figure 2
Synthetic methodologies for the preparation of oxazinanone moiety.
Figure 3
Figure 3
Synthesis of 1,3-oxazinane-2,5-diones from diazo carbonyl moieties. (A) Through rhodium catalyzed N-H insertion reaction; (B) through scandium triflate (Sc(OTf)3) catalyzed insertion reaction; (C) through an indium triflate [In(OTf)3] catalyzed intramolecular cyclization reaction; (D) through silica-supported HClO4 catalyzed intramolecular cyclization reaction.
Scheme 1
Scheme 1
Preparation of N-Cbz-protected diazo carbonyls compounds 1 and 3–11.
Scheme 2
Scheme 2
Synthesis of oxazinanones from diazo carbonyls via silica-supported HClO4 catalysis.
Figure 4
Figure 4
A proposed mechanism for the synthesis of oxazinanones from diazo carbonyls through silica-supported HClO4 catalysis.
See this image and copyright information in PMC

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