A practical one-pot isoindolinone synthesis enabled by Rh III catalysis was developed. The advantage of this protocol is that it does not require pre-preparation of amide substrates, because Rh III participates in two reactions independently. This mild, operationally multicomponent process transforms a wide variety of commercially available aldehydes into the corresponding γ-lactams in good yields, thereby demonstrating that N-pyridin-2-yl benzamide is an effective directing group. Notably, the anxiolytic drugs pagoclone and pazinaclone can be directly prepared by this methodology.Letter pubs.acs.org/OrgLett

Fluoroalkylated alkenes are of significant importance in life sciences and functional materials. The fluoroalkylation of alkynes offers an efficient method for the synthesis of functionalized fluoroalkylated alkenes. However, the current methods are often limited to 1,2-difunctionalization, while the remote fluoroalkylative difunctionalization of alkynes has been rarely developed. Herein, a novel visible-light-induced remote halo-difluoroalkylation of thioalkynes is realized with difluoroalkyl halides as the radical source, forming distally halogenated (Z)-fluoroalkylated alkenes in moderate to high yields with excellent regio-, stereo-, and site-selectivity. The notable features of this reaction include the mild reaction conditions, broad substrate scope, concurrent formation of three new chemical bonds, and a thermodynamically less stable (Z)-alkene, thus enabling it a highly attractive method for organic synthesis. It represents a new advance on the direct C-H bond halogenation. Preliminary mechanistic studies indicate a cascade radical process involving the heteroatom-induced β-fluoroalkylation of C-C triple bonds, intramolecular 1,5-hydrogen atom transfer (1,5-HAT), single electron transfer (SET) oxidation and halide addition.

Divergent synthesis is a powerful strategy for the fast assembly of different molecular scaffolds from the identical starting materials. We describe here a solvent-controlled photocatalytic divergent cyclization of alkynyl aldehydes...

Divergent synthesis is a powerful strategy for the fast assembly of different molecular scaffolds from the identical starting materials. We describe here a novel solvent-controlled photocatalytic divergent cyclization of alkynyl aldehydes with sulfonyl chlorides for the direct construction of highly functionalized cyclopentenones and dihydropyranols that widely exist in bioactive molecules and natural products. Density functional theory calculations suggest that an unprecedented N,N-dimethylacetamide-assisted 1,2-hydrogen transfer of alkoxy radicals is responsible for the cyclopentenone formation, whereas a C-C cleavage accounts for the selective production of dihydropyranols in acetonitrile. Given the simple and mild reaction conditions, excellent functional group compatibility, forming up to four chemical bonds, and tunable selectivity, it may find wide applications in synthetic chemistry.