A general system achieving three-component intermolecular carbofunctionalization of alkenes is presented, including carboetherification, carboesterification, carboarylation, and carboamination. The scope of the reaction is presented with respect to the carbon electrophile, the olefin, and the nucleophile. Furthermore, the synthesis of γ-lactams a carboamination reaction is demonstrated in a telescoped three-step protocol.
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http://dx.doi.org/10.1021/acs.orglett.1c01180 | DOI Listing |
J Org Chem
January 2025
College of Chemistry and Chemical Engineering, Anyang Normal University, Anyang 455000, P. R. China.
Herein, we present a copper-catalyzed, three-component intermolecular 1,4-alkylarylation of 1,3-enynes with ethers and aryl boronic acids. This method, driven by α-C(sp)-H functionalization of the oxygen atom in ethers, regioselectively produces various tetrasubstituted allenes from simple, readily available precursors. Key features include mild reaction conditions and a simple catalytic system.
View Article and Find Full Text PDFOrg Lett
January 2025
Gansu International Scientific and Technological Cooperation Base of Water-Retention Chemical Functional Materials, Key Laboratory of Eco-Environment-Related Polymer Materials Ministry of Education, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu 730070, China.
Here, we present a three-component successive radical addition strategy for the preparation of complex noncanonical α-amino acids from easily available glycine derivatives, alkenes, and aryl sulfonium salts via a copper-catalyzed photoredox-neutral catalytic cycle. The utility of this method is further demonstrated by its application in late-stage site-selective modifications of glycine residues in short peptides. It is worth noting that only 1 mol % copper catalyst is required in this reaction, demonstrating high catalytic efficiency.
View Article and Find Full Text PDFOrg Lett
January 2025
Department of Chemistry, College of Science, China Agricultural University, 2 Yuanmingyuan West Road, Beijing 100193, P. R. China.
A three-component cascade boronation-dearomatization reaction of alkenes, a diboron compound, and a pyridinium salt is diclosed, affording chiral boron-containing 1,4-dihyropyridines in high yields (≤98%) and diastereoselectivity (≤10:1 dr), along with excellent enantioselectivity (typically >99% ee). The catalytic system performs efficiently at low catalyst loadings (1 mol %) and was tested with >50 examples, including some biologically active molecules.
View Article and Find Full Text PDFOrg Lett
December 2024
Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Faculty of Chemistry, Northeast Normal University, Changchun 130024, China.
A novel dual photoredox/copper-catalyzed three-component alkylcyanation of alkenes and 1,4-alkylcyanation of 1,3-enynes have been developed. In this radical cyanoalkylation reaction, the photoredox induced alkyl radical from sulfoxonium ylides adds to the carbon-carbon double bonds of styrenes or 1,3-enynes, and the generated benzylic or allenyl radicals couple with a Cu(II) cyanide complex to achieve selective cyanation. The reaction exhibits high chemo- and regioselectivity and a wide substrate scope, providing an efficient method for the synthesis of alkyl nitriles and allenyl nitriles in a single step.
View Article and Find Full Text PDFJ Org Chem
December 2024
Department of Chemistry, School of Science, Tianjin University, Tianjin 300072, China.
A one-pot, three-component synthesis of indole-benzofuran bis-heterocycles from terminal alkynes, salicylaldehydes, and indoles has been developed via copper-catalyzed tandem annulation. This catalytic system utilizes readily available starting materials, enabling predictable synthesis of indole-benzofuran bis-heterocycles with broad substrate versatility, excellent regiocontrol, and gram-scale amenability. The reaction proceeds via a sequential pathway involving A3 coupling, 1,4-conjugate addition, and 5-- cyclization.
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