A reaction of bromo- and iododifluoromethyl-substituted silanes with electron-deficient alkenes in the presence of an N-heterocyclic carbene borane complex is described. The reaction is performed under irradiation with light-emitting diodes and proceeds via a radical chain mechanism. The resulting products, the functionalized silicon reagents, can undergo chemoselective transformations involving either the silyldifluoromethyl fragment or the functional group.
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http://dx.doi.org/10.1021/acs.orglett.7b01334 | DOI Listing |
Molecules
December 2024
Department of Organic Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China.
In this study, an iridium-catalyzed selective 1,4-reduction of α,β-unsaturated carbonyl compounds is realized, with water as a solvent and formic acid as a hydride donor. The new efficient iridium catalyst features a 2-(4,5-dihydroimidazol-2-yl)quinoline ligand. The chemoselectivity and catalyst efficiency are highly dependent on the electronic and steric properties of the substrates.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, United States.
We report a Ni-catalyzed vicinal alkylarylation of unactivated alkenes in γ,δ- and δ,ε-alkenylamines with aryl halides and alkylzinc reagents. The reaction is enabled by amine coordination and can use all primary, secondary, and tertiary amines. The reaction constructs two new C(sp)-C(sp) and C(sp)-C(sp) bonds and produces δ- and ε-arylamines with C(sp)-branching at the γ- and δ-positions.
View Article and Find Full Text PDFChem Commun (Camb)
December 2024
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, 325035, P. R. China.
A selective green-light-induced hydroselenation of alkenes with diselenides using Hantzsch ester as the hydrogen donor has been developed. In the case of electron-neutral diaryl diselenides and diacyl ones, alkenes undergo anti-Markovnikov-selective hydroselenation. When switching to electron-deficient diaryl diselenides and dialkyl ones, Markovnikov-selective hydroselenation occurs.
View Article and Find Full Text PDFOrg Lett
December 2024
College of Chemistry, Zhengzhou University, Zhengzhou 450001, P. R. China.
NHC boryl radical mediated halogen atom transfer (XAT) is useful in organic synthesis. Yet, most of the reaction ends only with reducing the halogen to hydrogen, that is, the C-X to C-H. This is especially dominant for electron-deficient alkyl halides, where the formed electrophilic radical reacts rapidly with NHC boranes.
View Article and Find Full Text PDFChem Commun (Camb)
December 2024
Department of Chemistry, Graduate School of Science, Tohoku University, Aramaki, Aoba-ku, Sendai 980-8578, Japan.
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