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

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2021 Dec 7

PMID 34874602

Citations 6

Authors

Valentina Pelliccioli

Thierry Hartung

Martin Simon

Christopher Golz

Emanuela Licandro

Silvia Cauteruccio

Manuel Alcarazo

Affiliations

Soon will be listed here.

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.

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