Visible Light Uranyl Photocatalysis: Direct C–H to C–C Bond Conversion

Uranyl nitrate hexahydrate performs as an efficient photocatalyst in the direct C–H to C–C bond conversion under blue light irradiation via hydrogen atom transfer (HAT). This uranyl salt enables th..

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

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[Figure not available: see fulltext.

Site-Selective C–H Functionalization by Decatungstate Anion Photocatalysis: Synergistic Control by Polar and Steric Effects Expands the Reaction Scope

The synergistic control of the SH2 transition states of hydrogen abstraction by polar and steric effects provides a promising strategy in achieving site-selective C(sp3)–H functionalization under decatungstate anion photocatalysis. By using this photocatalytic approach, the C–H bonds of alkanes, alcohols, ethers, ketones, amides, esters, nitriles, and pyridylalkanes were functionalized site-selectively. In the remarkable case of a 2,4-disubstituted cyclohexanone bearing five methyl, five methylene, and three methine C–H bonds, one methine C–H bond in the isoamyl tether was selectively functionalized

Sunlight Photocatalyzed Regioselective β‐Alkylation and Acylation of Cyclopentanones.

Visible light induced direct β-C–H/C–C conversion of cyclopentanones was accomplished by using tetrabutylammonium decatungstate, TBADT, as the photocatalyst

Versatile Cross-Dehydrogenative Coupling of Heteroaromatics and Hydrogen Donors via Decatungstate Photocatalysis

A facile sunlight-induced derivatization of heteroaromatics via photocatalyzed C-H functionalization in amides, ethers, alkanes and aldehydes is described. Tetrabutylammonium decatungstate (TBADT) was used as the photocatalyst and allowed to carry out the process under mild conditions

Generation of Alkyl Radicals:From the Tyranny of Tin to the Photon Democracy

Alkyl radicals are key intermediates in organic synthesis. Their classic generation from alkyl halides has a severe drawback due to the employment of toxic tin hydrides to the point that "flight from the tyranny of tin"in radical processes was considered for a long time an unavoidable issue. This review summarizes the main alternative approaches for the generation of unstabilized alkyl radicals, using photons as traceless promoters. The recent development in photochemical and photocatalyzed processes enabled the discovery of a plethora of new alkyl radical precursors, opening the world of radical chemistry to a broader community, thus allowing a new era of photon democracy

Metal-free photocatalytic cross-electrophile coupling enables C1 homologation and alkylation of carboxylic acids with aldehydes

Authors are grateful to have received generous funding from the European Union H2020 research and innovation program under the Marie S. Curie Grant Agreement (PhotoReAct, No 956324, S.B., M.L., A.L., G.M., E.Z.C., T.N.; CHAIR, No 860762, A.P., M.J., T.N.)In contemporary drug discovery, enhancing the sp3-hybridized character of molecular structures is paramount, necessitating innovative synthetic methods. Herein, we introduce a deoxygenative cross-electrophile coupling technique that pairs easily accessible carboxylic acid-derived redox-active esters with aldehyde sulfonyl hydrazones, employing Eosin Y as an organophotocatalyst under visible light irradiation. This approach serves as a versatile, metal-free C(sp3)−C(sp3) cross-coupling platform. We demonstrate its synthetic value as a safer, broadly applicable C1 homologation of carboxylic acids, offering an alternative to the traditional Arndt-Eistert reaction. Additionally, our method provides direct access to cyclic and acyclic β-arylethylamines using diverse aldehyde-derived sulfonyl hydrazones. Notably, the methodology proves to be compatible with the late-stage functionalization of peptides on solid-phase, streamlining the modification of intricate peptides without the need for exhaustive de-novo synthesis.Peer reviewe