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

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 1,12-Disubstituted [4]Helicenes.

A highly enantioselective synthesis of 1,12-disubstituted [4]carbohelicenes is reported. The key step for the developed synthetic route is a Au-catalyzed intramolecular alkyne hydroarylation, which is achieved with good to excellent regio- and enantioselectivity by employing TADDOL-derived (TADDOL=α,α,α,α-tetraaryl-1,3-dioxolane-4,5-dimethanol) α-cationic phosphonites as ancillary ligands. Moreover, an appropriate design of the substrate makes the assembly of [4]helicenes of different substitution patterns possible, thus demonstrating the synthetic utility of the method. The absolute stereochemistry of the newly prepared structures was determined by X-ray crystallography and characterization of their photophysical properties is also reported.

Enantioselective Synthesis of 1-Aryl Benzo[5]helicenes Using BINOL-Derived Cationic Phosphonites as Ancillary Ligands.

The synthesis of unprecedented BINOL-derived cationic phosphonites is described. Through the use of these phosphanes as ancillary ligands in AuI catalysis, a highly regio- and enantioselective assembly of appropriately designed alkynes into 1-(aryl)benzo[5]carbohelicenes is achieved. The modular synthesis of these ligands and the enhanced reactivity that they impart to AuI -centers after coordination have been found to be the key features that allow an optimization of the reaction conditions until the desired benzo[5]helicenes are obtained with high yield and enantioselectivity.