Chiral Near-Infrared Fluorophores by Self-Promoted Oxidative Coupling of Cationic Helicenes with Amines/Enamines
Corresponding Author
Dr. Johann Bosson
Department of Organic Chemistry, University of Geneva, Quai Ernest Ansermet 30, 1211 Geneva 4, Switzerland
Search for more papers by this authorGeraldine M. Labrador
Department of Organic Chemistry, University of Geneva, Quai Ernest Ansermet 30, 1211 Geneva 4, Switzerland
Search for more papers by this authorDr. Céline Besnard
Laboratoire de Cristallographie, University of Geneva, Quai Ernest Ansermet 24, 1211 Geneva 4, Switzerland
Search for more papers by this authorCorresponding Author
Prof. Denis Jacquemin
CEISAM UMR 6230, CNRS, University of Nantes, 44000 Nantes, France
Search for more papers by this authorCorresponding Author
Prof. Jérôme Lacour
Department of Organic Chemistry, University of Geneva, Quai Ernest Ansermet 30, 1211 Geneva 4, Switzerland
Search for more papers by this authorCorresponding Author
Dr. Johann Bosson
Department of Organic Chemistry, University of Geneva, Quai Ernest Ansermet 30, 1211 Geneva 4, Switzerland
Search for more papers by this authorGeraldine M. Labrador
Department of Organic Chemistry, University of Geneva, Quai Ernest Ansermet 30, 1211 Geneva 4, Switzerland
Search for more papers by this authorDr. Céline Besnard
Laboratoire de Cristallographie, University of Geneva, Quai Ernest Ansermet 24, 1211 Geneva 4, Switzerland
Search for more papers by this authorCorresponding Author
Prof. Denis Jacquemin
CEISAM UMR 6230, CNRS, University of Nantes, 44000 Nantes, France
Search for more papers by this authorCorresponding Author
Prof. Jérôme Lacour
Department of Organic Chemistry, University of Geneva, Quai Ernest Ansermet 30, 1211 Geneva 4, Switzerland
Search for more papers by this authorGraphical Abstract
Cationic dioxa[6]helicene oxidizes alkyl amines to enamines and further reacts in situ as an electrophile to form, in one-pot multi-step cascades, fully delocalized mono or bis donor-π-acceptor coupling products. This original approach provides chiral cyanine-like chromophores that absorb up to the NIR and fluoresce alike, with intense NIR ECD (Δϵ up to 60 M−1 cm−1). DFT showcases the importance of conformers in the strong chiroptical response.
Abstract
In one pot, tertiary alkyl amines are oxidized to enamines by cationic dioxa[6]helicene, which further reacts as electrophile and oxidant to form mono or bis donor-π-acceptor coupling products. This original and convergent synthetic approach provides a strong extension of conjugation yielding chromophores that absorb intensively in far-red or NIR domains (λmax up to 791 nm) and fluoresce in the NIR as well (λmax up to 887 nm). Intense ECD properties around 790 nm with a |Δϵ| value up to 60 M−1 cm−1 are observed.
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