Chiral Phosphathiahelicenes: Improved Synthetic Approach and Uses in Enantioselective Gold(I)-Catalyzed [2 + 2] Cycloadditions of N‑Homoallenyl Tryptamines

A chiral phosphathiahelicene scaffold displaying a phosphole and a thiophene unit as the terminal rings of the helical sequence has been synthesized and characterized by spectroscopic methods and X-ray diffraction studies. The phosphine oxides (HelPhos-V oxides) have been obtained following a robust...

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Bibliographic Details
Published in:ACS catalysis 2020-08, Vol.10 (15), p.8141-8148
Main Authors: Magné, Valentin, Sanogo, Youssouf, Demmer, Charles S, Retailleau, Pascal, Marinetti, Angela, Guinchard, Xavier, Voituriez, Arnaud
Format: Article
Language:English
Subjects:
Catalysis
Chemical Sciences
Organic chemistry
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Summary:A chiral phosphathiahelicene scaffold displaying a phosphole and a thiophene unit as the terminal rings of the helical sequence has been synthesized and characterized by spectroscopic methods and X-ray diffraction studies. The phosphine oxides (HelPhos-V oxides) have been obtained following a robust and scalable synthetic approach, based on a nickel-promoted alkyne cyclotrimerization reaction. Then, late-stage functionalization has been carried out via a bromination/palladium coupling reaction sequence. The HelPhos-V gold­(I) complexes have been used as catalysts in the unprecedented enantioselective [2 + 2] cyclization of N-homoallenyl tryptamine derivatives, to afford indolenine-fused cyclobutanes in good isolated yields, with enantiomeric excesses up to 93%.
ISSN:2155-5435
2155-5435
DOI:10.1021/acscatal.0c01819