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. 2016 Jun 29;138(25):7808-11.
doi: 10.1021/jacs.6b03221. Epub 2016 Jun 16.

Enantioselective Intermolecular [2 + 2] Photocycloaddition Reactions of 2(1H)-Quinolones Induced by Visible Light Irradiation

Andreas Tröster  1 , Rafael Alonso  1 , Andreas Bauer  1 , Thorsten Bach  1
Affiliations

Enantioselective Intermolecular [2 + 2] Photocycloaddition Reactions of 2(1H)-Quinolones Induced by Visible Light Irradiation

Andreas Tröster et al. J Am Chem Soc. .

Abstract

In the presence of a chiral thioxanthone catalyst (10 mol %) the title compounds underwent a clean intermolecular [2 + 2] photocycloaddition with electron-deficient olefins at λ = 419 nm. The reactions not only proceeded with excellent regio- and diastereoselectivity but also delivered the respective cyclobutane products with significant enantiomeric excess (up to 95% ee). Key to the success of the reactions is a two-point hydrogen bonding between quinolone and catalyst enabling efficient energy transfer and high enantioface differentiation. Preliminary work indicated that solar irradiation can be used for this process and that the substrate scope can be further expanded to isoquinolones.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Previous Work on Enantioselective Intermolecular [2 + 2] Photocycloaddition Reactions
Scheme 2
Scheme 2. Apparatus for Solar Irradiation and Result of an Intermolecular [2 + 2] Photocycloaddition
Scheme 3
Scheme 3. Mechanistic Picture of the Enantioselective [2 + 2] Photocycloaddition and Origin for the Formation of Racemic Product rac-4
Scheme 4
Scheme 4. Competing Intermolecular [2 + 2] Photocycloaddition of Vinyl Acetate vs Ethyl Vinyl Ketone and 2(1H)-Quinolone
Scheme 5
Scheme 5. Enantioselective Intermolecular [2 + 2] Photocycloaddition of 1(2H)-Isoquinolone and Methyl Vinyl Ketone
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