Site-Selective γ-Trihalomethylation and γ-Dihalomethylidenation of Silyl Dienol Ethers under Organophotoredox Catalysis.

We report a general remote tribromo- and trichloromethylation process using CBr and CBrCl as ready available sources of trihalomethyl radicals. This method operates under mild and metal-free photocatalyzed conditions and enables the access to γ-trihalomethylated enals with complete regioselectivity in up to 71 % isolated yield. Importantly, this protocol is easily adapted to the selective one-pot synthesis of the corresponding γ-dihalomethylidenated enals in up to 49 % overall yield.

Dearomatization of Pyridines: Photochemical Skeletal Enlargement for the Synthesis of 1,2-Diazepines.

In this report, we developed a unified and standardized one-pot sequence that converts pyridine derivatives into 1,2-diazepines by inserting a nitrogen atom. This skeletal transformation capitalizes on the generation of 1-aminopyridinium ylides, which rearrange under UV light irradiation. A thorough evaluation of the key parameters (wavelength, reaction conditions, activating agent) allowed us to elaborate on a simple, mild, and user-friendly protocol.

Highly selective γ-alkoxylation, γ-amination and γ-alkylation of unbiased enals by means of photoredox catalysis.

We report herein a general and highly selective γ-functionalization protocol under visible light irradiation. This mild radical approach enables the expansion of the scope of application to unbiased enals and the introduction of a wide variety of alkoxy, amino and alkyl functionalities in the γ position with complete regioselectivity.

Remote Radical Trifluoromethylation: A Unified Approach to the Selective Synthesis of γ-Trifluoromethyl α,β-Unsaturated Carbonyl Compounds.

Site-selective trifluoromethylation of silyl dienol ethers derived from α,β-unsaturated aldehydes, ketones, and amides was achieved for the first time in the remote γ position. This photoredox catalyzed process is quite general to compounds bearing many functionalities and is applicable to the late-stage functionalization of biorelevant molecules. The use of -perfluoroalkyl sulfoximines as ·R radical sources enables the generalization of the reaction to other perfluoroalkyl groups (R = CFH, CF).

Chloride Binding Modulated by Anion Receptors Bearing Tetrazine and Urea.

Modulation and fine-tuning of the strength of weak interactions to bind anions are described in a series of synthetic receptors. The general design of the receptors includes both a urea motif and a tetrazine motif. The synthetic sequence towards three receptors is detailed.