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Mechanistic Studies on the Cu-Catalyzed Three-Component Reactions of Sulfonyl Azides, 1-Alkynes and Amines, Alcohols, or Water: Dichotomy via a Common Pathway

Yoo, Eun Jeong ; Ahlquist, Mårten ; Bae, Imhyuck ; Sharpless, K. Barry ; Fokin, Valery V ; Chang, Sukbok

Journal of organic chemistry, 2008-07, Vol.73 (14), p.5520-5528 [Periódico revisado por pares]

Washington, DC: American Chemical Society

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Título:
Mechanistic Studies on the Cu-Catalyzed Three-Component Reactions of Sulfonyl Azides, 1-Alkynes and Amines, Alcohols, or Water: Dichotomy via a Common Pathway
Autor: Yoo, Eun Jeong ; Ahlquist, Mårten ; Bae, Imhyuck ; Sharpless, K. Barry ; Fokin, Valery V ; Chang, Sukbok
Assuntos: Alcohols - chemistry ; Alkynes - chemistry ; Amines - chemistry ; Azides - chemistry ; Catalysis ; Chemistry ; Copper - chemistry ; Ethylenes - chemistry ; Exact sciences and technology ; Heterocyclic compounds ; Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings ; Imidoesters - chemistry ; Isomerism ; Ketones - chemistry ; Kinetics ; Kinetics and mechanisms ; Models, Molecular ; Molecular Structure ; Organic chemistry ; Preparations and properties ; Reactivity and mechanisms ; Sulfur Compounds - chemistry ; Temperature ; Triazoles - chemistry ; Water - chemistry
É parte de: Journal of organic chemistry, 2008-07, Vol.73 (14), p.5520-5528
Notas: ark:/67375/TPS-V2X0V7X9-3
Experimental details of the product distribution, trapping studies, kinetic studies, characterization, copies of 1H and 13C NMR spectra of the newly obtained products (5) in the present studies, X,Y,Z coordinates for the calculated compounds/transition states, and energies of the respective geometries. This material is available free of charge via the Internet at http://pubs.acs.org.
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Descrição: Combined analyses of experimental and computational studies on the Cu-catalyzed three-component reactions of sulfonyl azides, terminal alkynes and amines, alcohols, or water are described. A range of experimental data including product distribution ratio and trapping of key intermediates support the validity of a common pathway in the reaction of 1-alkynes and two distinct types of azides substituted with sulfonyl and aryl(alkyl) groups. The proposal that bimolecular cycloaddition reactions take place initially between triple bonds and sulfonyl azides to give N-sulfonyl triazolyl copper intermediates was verified by a trapping experiment. The main reason for the different outcome from reactions between sulfonyl and aryl(alkyl) azides is attributed to the lability of the N-sulfonyl triazolyl copper intermediates. These species are readily rearranged to another key intermediate, ketenimine, into which various nucleophiles such as amines, alcohols, or water add to afford the three-component coupled products: amidines, imidates, or amides, respectively. In addition, the proposed mechanistic framework is in good agreement with the obtained kinetics and competition studies. A computational study (B3LYP/LACV3P*+) was also performed confirming the proposed mechanistic pathway that the triazolyl copper intermediate plays as a branching point to dictate the product distribution.
Editor: Washington, DC: American Chemical Society
Idioma: Inglês

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Mechanistic Studies on the Cu-Catalyzed Three-Component Reactions of Sulfonyl Azides, 1-Alkynes and Amines, Alcohols, or Water: Dichotomy via a Common Pathway

Yoo, Eun Jeong ; Ahlquist, Mårten ; Bae, Imhyuck ; Sharpless, K. Barry ; Fokin, Valery V ; Chang, Sukbok

Washington, DC: American Chemical Society

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