A highly enantioselective synthesis of 5,13-disubstituted dibenzo[d,d′]benzo[1,2-b:4,3-b′]dithiophenes is reported. Key for the successful assembly of these helical architectures is the last two successive Au-catalyzed intramolecular alkyne hydroarylation events. Specifically, the second cyclization is the enantiodetermining step of the whole process and provides the desired helicenes with excellent ee values when a TADDOL-derived 1,2,3-(triazolium)phosphonite moiety (TADDOL: α,α,α′,α′-tetraaryl-1,3-dioxolane-4,5-dimethanol) is employed as an ancillary ligand. The absolute stereochemistry of the newly prepared structures has been determined by X-ray crystallography to be P; the optical properties of these heterohelicenes are also reported. A three-step procedure was subsequently developed that allows the transformation of the initially obtained dithia[5]helicenes into dithia[9]helicenes without erosion of the enantiopurity.

Enantioselective Synthesis of Dithia[5]helicenes and their Postsynthetic Functionalization to Access Dithia[9]helicenes / V. Pelliccioli, T. Hartung, M. Simon, C. Golz, E. Licandro, S. Cauteruccio, M. Alcarazo. - In: ANGEWANDTE CHEMIE. INTERNATIONAL EDITION. - ISSN 1433-7851. - 61:6(2022 Feb 01), pp. e202114577.1-e202114577.6. [10.1002/anie.202114577]

Enantioselective Synthesis of Dithia[5]helicenes and their Postsynthetic Functionalization to Access Dithia[9]helicenes

V. Pelliccioli
Primo
;
E. Licandro;S. Cauteruccio
Penultimo
;
2022

Abstract

A highly enantioselective synthesis of 5,13-disubstituted dibenzo[d,d′]benzo[1,2-b:4,3-b′]dithiophenes is reported. Key for the successful assembly of these helical architectures is the last two successive Au-catalyzed intramolecular alkyne hydroarylation events. Specifically, the second cyclization is the enantiodetermining step of the whole process and provides the desired helicenes with excellent ee values when a TADDOL-derived 1,2,3-(triazolium)phosphonite moiety (TADDOL: α,α,α′,α′-tetraaryl-1,3-dioxolane-4,5-dimethanol) is employed as an ancillary ligand. The absolute stereochemistry of the newly prepared structures has been determined by X-ray crystallography to be P; the optical properties of these heterohelicenes are also reported. A three-step procedure was subsequently developed that allows the transformation of the initially obtained dithia[5]helicenes into dithia[9]helicenes without erosion of the enantiopurity.
Alkyne hydroarylation; Asymmetric catalysis; Au-catalysis; Dithia[5]helicenes; π-Extension;
Settore CHIM/06 - Chimica Organica
1-feb-2022
7-dic-2021
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/922147
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