Herein, we report a three-component organophotoredox coupling of -alkenyl amides with α-bromocarbonyls and various nucleophiles. This transition metal-free difunctionalization protocol installs sequential C-C and C-Y (Y = S/O/N) bonds in alkenes. This reaction works with terminal and internal alkenes containing both cyclic and acyclic amides radical-polar crossover.
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http://dx.doi.org/10.1039/d2cc04101d | DOI Listing |
Angew Chem Int Ed Engl
December 2024
Key Laboratory of Organic Synthesis of Jiangsu Province, MOE Key Laboratory of Geriatric Diseases and Immunology, Suzhou Key Laboratory of Pathogen Bioscience and Anti-infective Medicine, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 215123, Suzhou, China.
A regioselective cobalt-catalyzed three-component silylamidation that rapidly and reliably incorporates dioxazolones and silylzinc pivalates into unconjugated alkenyl amides is disclosed. Notably, the unique power of this protocol is demonstrated by the possibility of achieving peptide ligation using peptide-containing dioxazolones or alkenyl amides as the coupling partners. Moreover, this approach is distinguished by its mild condition, synthetic simplicity, and ample scope, thus providing a new platform for modular access to silicon-containing amino acid derivatives and peptides.
View Article and Find Full Text PDFJ Org Chem
January 2025
Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan.
Using amines in catalytic transfer hydrogenation (TH) is challenging, despite their potential availability as a hydrogen source. Here, we describe a photoredox/nickel-catalyzed TH of alkyne through an intermediary aminoalkyl Ni species. This reaction successfully provided functionalized ()-alkenes, such as (homo)allyl ethers, alcohols, and amides (/ = up to >99:1), and the reaction thus bypasses a limitation of substrate scope in TH using amine and a Lindlar catalyst.
View Article and Find Full Text PDFOrg Lett
December 2024
Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon 34141, South Korea.
Enamides have emerged as robust alternatives for enamines, exhibiting versatile reactivity for further synthetic modifications, including nucleophilic addition, cycloaddition, and asymmetric hydrogenation. While transition-metal-catalyzed cross-coupling of alkenyl (pseudo)halides with amides has been widely employed to construct this valuable scaffold, it suffers from some limitations, such as the need for transition-metal catalysts and the preparative synthesis of alkenyl (pseudo)halides. In this study, we report a mild and convenient stereoretentive decarboxylative amidation of α,β-unsaturated carboxylic acids with easily procurable 1,4,2-dioxazol-5-ones, providing a practical synthetic route to enamides.
View Article and Find Full Text PDFNat Commun
November 2024
State Key Laboratory of Organometallic Chemistry and Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences (CAS), Shanghai, PR China.
The transition metal-catalysed dicarbofunctionalisation of unactivated alkenes normally requires exogenous strong coordinated directing groups, thus reducing the overall reaction efficiency. Here, we report a ligand-enabled Ni(II)-catalysed dicarbofunctionalisation of unactivated alkenes with aryl/alkenyl boronic acids and alkyl halides as the coupling partners with a diverse range of native functional groups as the directing group. This dicarbofunctionalisation protocol provides an efficient and direct route towards vicinal 1,2-disubstituted alkanes using primary, secondary, tertiary amides, sulfonamides, as well as secondary and tertiary amines under redox-neutral conditions that are challenging to access through conventional methods.
View Article and Find Full Text PDFNat Commun
November 2024
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, PR China.
Photocatalytic N-to-C aryl migration allows for quick construction of highly useful amide derivatives from readily available compounds. By developing the reactions of sodium sulfinates with the N-aryl-propiolamides, we herein demonstrate that the CO-promoted visible-light-induced method enables a large variety of aryl groups on nitrogen atoms of the N-arylamides to undergo efficient aryl migration from N atom to C atom to synthesize tetra- and tri-substituted alkenyl amides selectively. 1,4-N-to-C aryl migration is a key step in this transformation which is achieved through photocatalytic radical-polar crossover pathway.
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