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Mn(I)-Catalyzed synthesis of seven- or eight-membered carbocycles is disclosed via C–H activation of heteroarenes and coupling with alkyne-functionalized 1,3-cyclopentadiones or 1,3-cyclohexadiones. This n to n + 2 (n = 5, 6) ring expansion reaction proceeded via a C–H alkenylation/carbonyl addition/retro-Aldol cascade. Structurally diverse mid-sized carbocycles were constructed via cleavage of both C–H and C–C bonds in a single operation. [ABSTRACT FROM AUTHOR]

Rhodium(iii)-catalyzed mild benzylic α-fluoroalkenylation of 8-methylquinolines with gem-difluorostyrenes has been developed. This reaction occurred via C–H activation and C–F cleavage and is applicable to a wide range of substrates, leading to the synthesis of Z-alkenyl fluorides under mild and redox-neutral conditions with high regio- and stereoselectivity. [ABSTRACT FROM AUTHOR]

The alkenylation reactions of 8-methylquinolines with alkynes, catalyzed by [{Cp*RhCl2}2], proceeds efficiently to give 8-allylquinolines in good yields by C(sp3)H bond activation. These reactions are highly regio- and stereoselective. A catalytically competent five-membered rhodacycle has been structurally characterized, thus revealing a key intermediate in the catalytic cycle. [ABSTRACT FROM AUTHOR]