The treatment of a variety of hydrosilanes, each incorporating a benzylic C(sp(3))-H bond, with a rhodium catalyst resulted in intramolecular dehydrogenative silylation. This silylation reaction was found to occur at typically unreactive C(sp(3))-H bonds located at terminal positions on alkyl chains. Interestingly, the rhodium catalyst also promoted regioselective silylation at a site internal to an alkyl chain.
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http://dx.doi.org/10.1021/ol303353m | DOI Listing |
Chem Commun (Camb)
June 2020
Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers, CNRS, Superacid Group in Organic Synthesis Team, F-86073 Poitiers, France.
The superacid-promoted electrophilic Csp3-H bond activation of aliphatic amines generates superelectrophilic species that can be subsequently fluorinated. Demonstrated by low-temperature in situ NMR experiments, the ammonium-carbenium dications, crucial for this reaction, can also react with C-H bonds opening future synthesis perspectives for this mode of activation.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
June 2017
Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.
An unprecedented method that makes use of the cooperative interplay between molecular iodine and photoredox catalysis has been developed for dual light-activated intramolecular benzylic C-H amination. Iodine serves as the catalyst for the formation of a new C-N bond by activating a remote Csp3 -H bond (1,5-HAT process) under visible-light irradiation while the organic photoredox catalyst TPT effects the reoxidation of the molecular iodine catalyst. To explain the compatibility of the two involved photochemical steps, the key N-I bond activation was elucidated by computational methods.
View Article and Find Full Text PDFOrg Lett
August 2016
School of Chemistry and Chemical Engineering, Guangdong Pharmaceutical University, Zhongshan 528458, China.
An efficient copper-catalyzed selective cross coupling of imidazo[1,2-a]pyridines with methyl hetarenes has been reported. This transformation opened a new route to synthesize the C-3 carbonyl imidazo[1,2-a]pyridine derivative, which is a common structural motif in natural products and pharmaceuticals. (18)O-labeling experiments indicated that the oxygen source of products originated from O2.
View Article and Find Full Text PDFChemistry
June 2016
Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397, Marseille, France.
A straightforward synthesis of air- and water-stable bis-cationic macrocyclic imidazolylboronium anion receptors is described herein. By taking advantage of the bulky and rigid 9-borabicyclo[3.3.
View Article and Find Full Text PDFOrg Lett
November 2015
Department of Chemistry, Indian Institute of Technology Guwahati, North Guwahati-781039, India.
Intermolecular C-N bond formations via cross-dehydrogenative coupling (CDC) of aryl ethers and tetrazoles have been developed under a metal-free condition. In the presence of catalytic amount of tetrabutylammonium iodide (TBAI) and aqueous TBHP, aryl ethers coupled efficiently with tetrazoles to afford hemiaminal ethers. This strategy showed high level of regioselectivity for substrates possessing multiple sp(3) C-H bonds adjacent to the ethereal oxygen.
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