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Literature DB >> 34775550

Aryl-Cl vs heteroatom-Si bond cleavage on the route to the photochemical generation of σ,π-heterodiradicals.

Lorenzo Di Terlizzi¹, Francesca Roncari¹, Stefano Crespi², Stefano Protti¹, Maurizio Fagnoni³.

Abstract

The photochemistry of aryl chlorides having a X-SiMe3 group (X = O, NR, S, SiMe2) tethered to the aromatic ring has been investigated in detail, with the aim to generate valuable ϭ,π-heterodiradicals. Two competitive pathways arising from the excited triplet state of the aromatics have been observed, namely heterolysis of the aryl-chlorine bond and homolysis of the X-silicon bond. The former path is found in chlorinated phenols and anilines, whereas the latter is exclusive in the case of silylated thiophenols and aryl silanes. A combined experimental/computational approach was pursued to explain such a photochemical behavior.Graphical abstract.

Entities: Chemical

Keywords: Aryl cations; Aryl chlorides; Heterodiradicals; Photoheterolysis; Photohomolysis

Mesh：

Substances：
Chlorides

Year: 2021 PMID： 34775550 DOI： 10.1007/s43630-021-00119-6

Source DB: PubMed Journal: Photochem Photobiol Sci ISSN： 1474-905X Impact factor: 4.328

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Aryl-Cl vs heteroatom-Si bond cleavage on the route to the photochemical generation of σ,π-heterodiradicals.

1. Recent advances in transition-metal-free carbon-carbon and carbon-heteroatom bond-forming reactions using arynes.

2. Antitumor antibiotics: bleomycin, enediynes, and mitomycin.

3. Parallel syntheses of (+)- and (-)-alpha-cuparenone by radical combination in crystalline solids.

4. Total synthesis of the antibiotic kendomycin by macrocyclization using photo-Fries rearrangement and ring-closing metathesis.

5. Taming Radical Pairs in Nanocrystalline Ketones: Photochemical Synthesis of Compounds with Vicinal Stereogenic All-Carbon Quaternary Centers.

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