Photoassisted Synthesis of Complex Molecular Architectures: Dearomatization of Benzenoid Arenes with Aza-o-xylylenes via an Unprecedented [2+4] Reaction Topology

Dmitry M Kuznetsov; Olga A Mukhina; Andrei G Kutateladze

doi:10.1002/anie.201602288

Photoassisted Synthesis of Complex Molecular Architectures: Dearomatization of Benzenoid Arenes with Aza-o-xylylenes via an Unprecedented [2+4] Reaction Topology

Angew Chem Int Ed Engl. 2016 Jun 6;55(24):6988-91. doi: 10.1002/anie.201602288. Epub 2016 Apr 21.

Authors

Dmitry M Kuznetsov¹, Olga A Mukhina¹, Andrei G Kutateladze²

Affiliations

¹ Department of Chemistry and Biochemistry, University of Denver, 2190 E. Iliff Ave., Denver, CO, 80208, USA.
² Department of Chemistry and Biochemistry, University of Denver, 2190 E. Iliff Ave., Denver, CO, 80208, USA. akutatel@du.edu.

Abstract

A new method was developed for the photoinduced dearomatization of arenes through an intramolecular cycloaddition with aza-o-xylylenes generated by excited-state intramolecular proton transfer (ESIPT) in the readily available photoprecursors. The [2+4] topology of this cycloaddition is unprecedented for photo-dearomatizations of benzenoid aromatic carbocycles. It provides rapid access to novel heterocycles, cyclohexadieno-oxazolidino-quinolinols, as valuable synthons for a broad range of post-photochemical transformations.

Keywords: [2+4] reactions; aza-o-xylylenes; dearomatization; photochemistry; polyheterocycles.

Publication types

Research Support, N.I.H., Extramural

MeSH terms

Aza Compounds / chemistry*
Benzene Derivatives / chemistry*
Cycloaddition Reaction
Heterocyclic Compounds / chemical synthesis*
Heterocyclic Compounds / chemistry
Hydroxyquinolines / chemical synthesis*
Hydroxyquinolines / chemistry
Molecular Structure
Photochemical Processes
Stereoisomerism
Xylenes / chemistry*

Substances

Aza Compounds
Benzene Derivatives
Heterocyclic Compounds
Hydroxyquinolines
Xylenes

Grants and funding

R15 GM093930/GM/NIGMS NIH HHS/United States