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Chemoselective Preparation of 1-Iodoalkynes, 1,2-Diiodoalkenes, and 1,1,2-Triiodoalkenes Based on the Oxidative Iodination of Terminal Alkynes
Published on: September 12, 2018
Mechanistic insights and enhanced reactivity of heteroleptic quinoline-based iodine(I) complexes
Sharath Mohan1, Jessica Rumfeldt1, Aaron Mailman1
1Department of Chemistry, University of Jyvaskyla, Jyväskylä, Finland.
Abstract:
The resurgence of heteroleptic halogen(I) complexes has provided a contender to the homoleptic halogen(I) reagents that currently dominate the field as halogenation reagents. In this work, a series of homoleptic [I(L)2]PF6, and heteroleptic iodine(I) carboxylate complexes have been synthesised utilising quinoline (L = Qu) and five 7-substituted quinoline derivatives (L= QuR; R = Cl, Br, Ph, Tol, Xyl) as the ligands in iodine(I) complexes of 4-trifluoromethylbenzoate, 1-L, and iodine(I) 2,3,4,5,6-pentafluorobenzoate, 2-L. Herein, it is shown that these heteroleptic iodine(I) complexes encompass the longest I···N bond lengths of any iodine(I) complex to date and therefore represent promising iodination reagents, which was confirmed experimentally by reaction of 2-Qu and [I(Qu)2]PF6 with a range of substrates, giving yields equal to Barluenga's reagent in a fraction of the reaction time. The iodination and UV-Vis spectroscopy studies were also utilised to probe the currently ambiguous reaction mechanism of stabilised iodine(I) carboxylates as iodination reagents, providing the first mechanistic insights for these heteroleptic iodine(I) complexes.
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