An efficient and practical strategy was developed to synthesize 1,3,4-triaryl-6-trifluoromethylpyridones from CF3-imidoyl sulfoxonium ylides and cyclopropenones in good to excellent yields. This stepwise [3 + 3] annulation reaction was carried out under transition-metal-, additive-, and solvent-free conditions, generating 1 equiv of dimethyl sulfoxide as byproduct and tolerating a series of functional groups.

A lithium-bromide-promoted nucleophilic substitution/ annulation cascade reaction between CF 3 -imidoyl sulfoxonium ylides and 1,3-dicarbonyl compounds has been established, and the corresponding 1,2,3-trisubstituted 5-trifluoromethylpyrroles have been obtained in 27−78% yield. This reaction features a broad substrate scope and generates dimethyl sulfoxide and H 2 O as byproducts. * sı Supporting InformationThe Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.orglett.1c02598.Optimization experiments, general experimental procedures, crystallographic data, and NMR spectra for new compounds (PDF)Accession Codes CCDC 2074418−2074420 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk

A ruthenium(II)-catalyzed C−H activation/annulation reaction of benzoic acids and CF3-imidoyl sulfoxonium ylides enabled by weak O-coordination has been achieved. A series of 3-trifluoromethylisoquinolinones were synthesized in 37-75% yields under redox-neutral...

The direct cleavage of C(CO)−C single bonds, delivering otherwise inaccessible compounds, is a significant challenge. Although the transition metal-catalyzed insertion of functional groups into C(CO)−C bonds has been studied, strained ketone substrates or chelating assistance were commonly required. In this article, we describe a rhodium(II)-catalyzed three-component reaction of 1,3-diones, diazoesters, and N,N -dimethylformamide (DMF), leading to an unusual formal insertion of O–C(sp 3 )–C(sp 2 ) into unstrained C(CO)−C bonds. This procedure provides a rapid entry to a gamut of otherwise inaccessible α,α,α-trisubstituted esters/amide from relatively simple substrates in a straightforward manner. 55 examples of highly decorated products demonstrate the broad functional group tolerance and substrate scope. The combination of control experiments and isotope-labeling reactions support that O, C(sp 3 ), and C(sp 2 ) units derive from 1,3-diones, diazoesters, and DMF, respectively.

We disclose a direct C(sp)−, C(sp 2 )−, and C(sp 3 )−H thiolation reaction using β-sulfinylesters as the versatile sulfur source.The key step of this protocol is chemoselective C−S bond cleavage of the sulfonium salts that are formed in situ from the corresponding alkenes, alkynes, and 1,3-dicarboxyl compounds with β-sulfinylesters. The successful capture of the acrylate byproduct supports a retro-Michael reaction mechanism.