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A Modular Cascade Synthetic Strategy Toward Structurally Constrained Boron-Doped Polycyclic Aromatic Hydrocarbons.

ABSTRACT: A novel synthetic strategy was developed for the construction of difficult-to-access structurally constrained boron-doped polycyclic aromatic hydrocarbons (sc-B-PAHs) via a cascade reaction from the readily available ortho-aryl-substituted diarylalkynes. This domino process involves borylative cyclization, 1,4-boron migration and successive two-fold electrophilic borylation. Two types of sc-B-PAHs bearing B-doped [4]helicene (1 a-1 i) or BN-doped [4]helicene (1 n-1 t) and double [4]helicene (1 u-1 v) are constructed by this cascade reaction. Remarkably, this synthetic strategy is characterized by modest yields (20-50 %) and broad substrate scope (18 examples) with versatile functional group tolerance. The resultant sc-B-PAHs show good stability under ambient conditions and are thoroughly investigated by X-ray crystallography, UV/Vis absorption and fluorescence spectroscopy, and cyclic voltammetry. Interestingly enough, BN-doped [4]helicene 1 o forms a unique alternating π-stacked dimer of enantiomers within a helical columnar superstructure, while BN-doped double [4]helicene 1 u establishes an unprecedented π-stacked trimeric sandwich structure with a rare 2D lamellar π-stacking. The synthetic approach reported herein represents a powerful tool for the rapid generation of novel sc-B-PAHs, which are highly attractive for the elucidation of the structure-property relationship and for potential optoelectronic applications.

SUBMITTER: Zhang JJ

PROVIDER: S-EPMC9298420 | biostudies-literature | 2021 Dec

REPOSITORIES: biostudies-literature

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A Modular Cascade Synthetic Strategy Toward Structurally Constrained Boron-Doped Polycyclic Aromatic Hydrocarbons.

Zhang Jin-Jiang JJ Yang Lin L Liu Fupin F Fu Yubin Y Liu Junzhi J Popov Alexey A AA Ma Ji J Feng Xinliang X

Angewandte Chemie (International ed. in English) 20211105 49

A novel synthetic strategy was developed for the construction of difficult-to-access structurally constrained boron-doped polycyclic aromatic hydrocarbons (sc-B-PAHs) via a cascade reaction from the readily available ortho-aryl-substituted diarylalkynes. This domino process involves borylative cyclization, 1,4-boron migration and successive two-fold electrophilic borylation. Two types of sc-B-PAHs bearing B-doped [4]helicene (1 a-1 i) or BN-doped [4]helicene (1 n-1 t) and double [4]helicene (1 u ...[more]

PMID: 34623744

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Project description:Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the environment as components of fossil fuels and by-products of combustion. These multi-ring chemicals differentially activate the Aryl Hydrocarbon Receptor (AHR) in a structurally-dependent manner, and induce toxicity via both AHR-dependent and -independent mechanisms. PAH exposure is known to induce developmental malformations in zebrafish embryos, and recent studies have shown cardiac toxicity induced by compounds with low AHR affinity. Unraveling the potentially diverse molecular mechanisms of PAH toxicity is essential for understanding the hazard posed by complex PAH mixtures present in the environment. We analyzed transcriptional responses to PAH exposure in zebrafish embryos exposed to benz(a)anthracene (BAA), dibenzothiophene (DBT) and pyrene (PYR) at a concentration that induces developmental malformations by 120 hours post-fertilization (hpf). Whole genome microarray analysis of mRNA expression at 24 and 48 hpf identified genes that were differentially regulated over time and in response to the three PAH structures. PAH body burden was analyzed at these time points using GC-MS, and demonstrated differences in PAH uptake into the embryos. This was important for discerning dose-related differences from those that represented unique molecular mechanisms. While BAA misregulated the smallest number of transcripts, it caused strong induction of cyp1a and other genes known to be downstream of the AHR, which were not induced by the other two PAHs. Analysis of functional roles of misregulated genes and their predicted regulatory transcription factors also distinguished the BAA response from regulatory networks disrupted by DBT and PYR exposure. These results indicate that systems approaches can be used to classify the toxicity of PAHs based on the networks perturbed following exposure and may provide a path for unraveling the toxicity of complex PAH mixtures. Gene expression was measured in zebrafish embryos after exposure to PAHs. Embryos were batch-exposed in groups of 40 to 25 μM BAA, 25 μM DBT, 25 μM PYR or 1% DMSO vehicle control starting at 6 hpf and collected at 24 or 48 hpf. Four independent biological replicates were prepared for each treatment. The reference was a pool of zebrafish embryos exposed to DMSO control until 24 and 48 hpf.

Dataset Information

A Modular Cascade Synthetic Strategy Toward Structurally Constrained Boron-Doped Polycyclic Aromatic Hydrocarbons.

Publications

A Modular Cascade Synthetic Strategy Toward Structurally Constrained Boron-Doped Polycyclic Aromatic Hydrocarbons.

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