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Enantioselective Recognition of Helicenes by a Tailored Chiral Benzo[ghi]perylene Trisimide π-Scaffold.

ABSTRACT: Enantioselective molecular recognition of chiral molecules that lack specific interaction sites for hydrogen bonding or Lewis acid-base interactions remains challenging. Here we introduce the concept of tailored chiral π-surfaces toward the maximization of shape complementarity. As we demonstrate for helicenes it is indeed possible by pure van-der-Waals interactions (π-π interactions and CH-π interactions) to accomplish enantioselective binding. This is shown for a novel benzo[ghi]perylene trisimide (BPTI) receptor whose π-scaffold is contorted into a chiral plane by functionalization with 1,1'-bi-2-naphthol (BINOL). Complexation experiments of enantiopure (P)-BPTI with (P)- and (M)-[6]helicene afforded binding constants of 10 700 M^-1 and 550 M^-1 , respectively, thereby demonstrating the pronounced enantiodifferentiation by the homochiral π-scaffold of the BPTI host. The enantioselective recognition is even observable by the naked eye due to a specific exciplex-type emission originating from the interacting homochiral π-scaffolds of electron-rich [6]helicene and electron-poor BPTI.

SUBMITTER: Teichmann B

PROVIDER: S-EPMC9303377 | biostudies-literature |

REPOSITORIES: biostudies-literature

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2015-10-01 | GSE51316 | GEO

Enantioselective Synthesis of 1,12-Disubstituted [4]Helicenes.

Project description: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=?,?,?,?-tetraaryl-1,3-dioxolane-4,5-dimethanol) ?-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.

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