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. 2023 Jan 10;26(2):e202201180.
doi: 10.1002/ejoc.202201180. Epub 2022 Dec 22.

Synthesis of 1,3-Dioxan-2-ones by Photo-Aerobic Selenium-π-Acid Multicatalysis

Kilian A Müller  1 , Carolin H Nagel  1 , Alexander Breder  1
Affiliations

Synthesis of 1,3-Dioxan-2-ones by Photo-Aerobic Selenium-π-Acid Multicatalysis

Kilian A Müller et al. European J Org Chem. .

Abstract

An expedient method for the synthesis of cyclic carbonates from homoallylic carbonic acid esters by means of photo-aerobic selenium-π-acid multicatalysis is reported. Until now, conceptually related methods commonly relied either on the stoichiometric addition of electrophiles onto the substrate's alkene moiety or the presence of pre-installed leaving groups in allylic position of said alkene to - in part, catalytically - initiate an intramolecular attack by an adjacent carbonic acid ester group. In sharp contrast, the current study shows that the C-C double bond of homoallylic carbonic acid esters can be directly activated by the catalytic interplay of a pyrylium dye and a diselane using ambient air as the sole oxidant and visible light as an energy source.

Keywords: 1,3-dioxan-2-ones; alkenes; allylic oxidation; photoredox catalysis; selenium-π-acid catalysis.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Carbonic acid esters in nature and synthetic methodology.
Scheme 2
Scheme 2
Conversion of homoallylic, primary carbonates 1 (n=1 mmol). Se‐Cat. 1=5 mol %; TAPT=5 mol %. Reaction time=24 h to 70 h, yields without brackets were determined by 1H NMR spectroscopy using 1,1,2,2‐tetrachloroethane as an internal standard. Yields with brackets refer to isolated compounds. [a] 1,3,5‐Trimethoxybenzene or 1,3‐nitrobenzene used as internal standards. [b] Reaction times longer than 70 h. All products 2 were obtained as E‐isomers.
Scheme 3
Scheme 3
Conversion of homoallylic, secondary carbonates 1 (n=1 mmol). Se‐Cat. 1=5 mol %; TAPT=5 mol %. Reaction time=37 h to 41 h, yields without brackets were determined by 1H NMR spectroscopy using 1,1,2,2‐tetrachloroethane as an internal standard. Yields with brackets refer to isolated compounds. Diastereomeric ratios (d. r.) were determined by 1H NMR spectroscopy of crude products. [a] Reaction times longer than 41 h. All products 2 were obtained as E‐isomers.
Scheme 4
Scheme 4
Mechanistic rationale for the observed cis‐diastereoselectivity under kinetic conditions.
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