A photocatalytic Smiles rearrangement, triggered by radical difluoromethylation of conjugated arylsulfonylated amides, was developed to construct both β-difluoromethyl amide and heterocyclic scaffolds selectively. This transformation features mild conditions and broad substrate scope. More importantly, the chemoselectivity of the intermediate amidyl radical could be altered completely by simply changing the light source, along with addition of water to the reaction mixture.
Key Laboratory of Environmentally Friendly Chemistry and Application of Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan, Hunan 411105, China.
We herein report a photochemical Truce-Smiles rearrangement reaction of -sulfinyl acrylamides with bromodifluoroacetamides resulting in the synthesis of a series of aryl difluoroglutaramides in moderate to good yields. The asymmetric synthesis using chiral sulfinamides produced quaternary carboncentered glutaramide products with a modest enantioselectivity. This protocol effectively complements previous Truce-Smiles rearrangement methods involving -sulfonyl acrylamides.
Cysteine (Cys) plays a critical role in various biological processes, including protein synthesis, cellular signaling, and antioxidant defense. However, precise detection of Cys in biological systems remains challenging due to interference from similar thiols such as homocysteine (Hcy) and glutathione (GSH). In this study, we report the synthesis and bioimaging of a novel ratio-type fluorescent probe based on the benzoBODIPY fluorophore, designed for the ratiometric detection of Cys.
Photocyclization of 8-aryloxy-3-phenylbenzo[][1,2,4]triazines leads to π-delocalized helicene radicals 1[n] ( = 5, 6, 7) containing the ring-fused 1,4-dihydro[1,2,4]triazin-4-yl as a spin source. Single crystal XRD revealed that the photocyclization to 1[n] involves a Smiles rearrangement. Radicals 1[n] were investigated by spectroscopic, electrochemical and DFT methods, while racemic helicene 1[7] was resolved and ECD spectra were recorded.
Institute of Green Chemistry and Molecular Engineering, GBRCE for Functional Molecular Engineering, Lehn Institute of Functional Materials, School of Chemistry, Sun Yat-sen University, Guangzhou 510006, PR China.
Radical Smiles rearrangements have emerged as powerful methodologies for constructing carbon-carbon bonds through intramolecular radical addition and fragmentation under milder conditions, with SO released as a byproduct. However, SO-retaining Smiles rearrangements, which can yield valuable alkyl sulfone derivatives, have been scarcely explored. In this study, we present an unprecedented iron-catalyzed SO-retaining Smiles rearrangement initiated by the decarboxylation of aliphatic carboxylic acids.
Herein we describe the synthesis and rearrangement of 1,3-diamino-2,7-naphthyridines and 1-amino-3-oxo-2,7-naphthyridines. In the case of 1,3-diamino-2,7-naphthyridines, it was found that the rearrangement reaction was influenced by both the substituent at the 7th position of the 2,7-naphthyridine ring and by the nature of the cyclic amine at the 1st position. The influence was mainly steric.
