Palladium(0)-catalyzed cyclopropane C-H bond functionalization: synthesis of quinoline and tetrahydroquinoline derivatives

A series of quinoline and tetrahydroquinoline derivatives were prepared via a one-pot protocol involving intramolecular palladium(0)-catalyzed cyclopropane sp3 C-H bond functionalization and subsequent oxidation or reduction. The reaction conditions demonstrate good tolerance for a wide range of functional groups. Evidence suggests that the reaction proceeds through C-H bond cleavage and C-C bond formation to generate a dihydroquinoline intermediate via in situ cyclopropane ring-opening. © 2012 The Royal Society of Chemistry

Diversity-oriented approach to CF3CHF-, CF3CFBr-, CF3CF2-, (CF3)2CH-, and CF3(SCF3)CH-substituted arenes from 1-(diazo-2,2,2-trifluoroethyl)arenes.

Arenes substituted with perfluoroalkyl groups are attractive targets for drug and agrochemical development. Exploiting the carbenic character of donor/acceptor diazo compounds, a diversity-oriented synthesis of perfluoroalkylated arenes, for late stage fluorofunctionalization, is described. The reaction of 1-(diazo-2,2,2-trifluoroethyl)arenes with HF, F/Br, F2, CF3H, and CF3SH sources give direct access to a variety of perfluoroalkyl-substituted arenes presenting with incremental fluorine content. The value of this approach is also demonstrated for radiochemistry and positron emission tomography with the [(18)F]-labeling of CF3CHF-, CF3CBrF-, and CF3CF2-arenes from [(18)F]fluoride