The exchange of the metal ion from Ni(II) to In(I) leads to a switch in the chemoselectivity of the [3 + 3] annulation of β,γ-unsaturated α-ketoesters and 1pyrazol-5-amines in the presence of phosphoric acid , affording functionalized 1pyrazolo[3,4-]pyridines in up to 97% yields and highly enantioselective 4,5-dihydro-1-pyrazolo[3,4-]pyridines in up to 92% yield and 99% ee.
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http://dx.doi.org/10.1021/acs.orglett.4c02529 | DOI Listing |
Org Lett
January 2025
Engineering Research Center of Tropical Medicine Innovation and Transformation of Ministry of Education, International Joint Research Center of Human-machine Intelligent Collaborative for Tumor Precision Diagnosis and Treatment of Hainan Province, Hainan Provincial Key Laboratory of Research and Development on Tropical Herbs, School of Pharmacy, Hainan Medical University, Haikou 571199, China.
A condition-controlled Rh(III)-catalyzed selective synthesis of CF-substituted indoles and pyrido[2,1-]isoindoles from 2-arylpyridines and CF-imidoyl sulfoxonium ylides has been developed. The Cp*Rh(MeCN)(SbF)/HFIP system afforded CF-substituted indoles via triple C-H activation, while the [Cp*RhCl]/MeCN condition selectively furnished CF-substituted pyrido[2,1-]isoindoles through C-H [4 + 1] annulation. The notable advantages of this developed method included readily available starting materials, broad substrate scope, and excellent chemoselectivity.
View Article and Find Full Text PDFAcc Chem Res
January 2025
Department of Chemistry and Chemistry Institution for Functional Materials, Pusan National University, Busan 46241, Republic of Korea.
ConspectusControlling selectivity through manipulation of reaction intermediates remains one of the most enduring challenges in organic chemistry, providing novel solutions for selective C-C π-bond functionalization. This approach, guided by activation principles, provides an effective method for selective functional group installation, enabling direct synthesis of organic molecules that are inaccessible through conventional pathways. In particular, the selective functionalization of N-conjugated allenes and alkynes has emerged as a promising research focus, driven by advances in controlling reactive intermediates and activation strategies.
View Article and Find Full Text PDFJ Org Chem
December 2024
School of Chemical and Environmental Engineering, Hunan Institute of Technology, Hengyang 421002, China.
An iron-catalyzed oxidative [3 + 3] annulation of oxime esters with inactivated saturated ketones is described. This cascade strategy allows one-step rapid synthesis of various structurally important pyridines through an oxidative dehydrogenation/annulation/oxidative aromatization sequence via direct α,β-dehydrogenation of simple saturated ketones followed by annulation with oximes. This method shows good functional group tolerance, readily accessible starting materials, a wide substrate scope, high chemoselectivity, and no need for extra stoichiometric oxidant and is also applicable to the late-stage functionalization of natural products.
View Article and Find Full Text PDFOrg Lett
October 2024
Tianjin Key Laboratory of Organic Solar Cells and Photochemical Conversion, Tianjin Key Laboratory of Drug Targeting and Bioimaging, School of Chemistry & Chemical Engineering, Tianjin University of Technology, Tianjin 300384, People's Republic of China.
A novel three-component [4 + 3] annulation reaction of isatin-derived azomethine ylides with azadienes was developed for the first time to efficiently synthesize spirooxindole-diazepines incorporating a benzothiophene moiety under catalyst-free conditions. Effects of the heteroatom of azadiene on the chemoselectivity was investigated. With the use of the azadiene bearing a benzofuran moiety as a substrate, the dominant reaction pathway was changed to an α-[3 + 2] annulation.
View Article and Find Full Text PDFOrg Lett
October 2024
Fluoro and Agrochemicals Division, CSIR-Indian Institute of Chemical Technology, Hyderabad, 500007, India.
The interaction of -alkoxy-1-indole-1-carboxamides with transition metals leads to indole-fused heterocyclic scaffolds through directing group leaving/migration, [3 + 2], N-C2 [4 + 1], and [4 + 2] annulations. However, the corresponding O-C2 [4 + 2] annulation reactions have never been reported. Herein, we report the chemoselective annulation of -alkoxy-1-indole-1-carboxamides catalyzed by Rh(III), affording [1,3]oxazinoindolones through a hitherto unknown reaction pathway.
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