Pt-catalyzed C-C activation induced by C-H activation.

The catalytic cleavage of two C-C single bonds is achieved by treatment of the hydrocarbon substrate spiro[bicyclo[2.2.1]hept-2-ene-7,1'-cyclopropane] with Pt(II) catalysts such as (Me2bpy)PtPh(NTf2) (Me2bpy = 4,4'-dimethyl-2,2'-bipyridine, NTf2(-) = N(SO2CF3)2(-)). The surprising rearrangement product 1,2,4,7,7a-pentahydroindene is generated in good yield. The mechanism of C-C bond activation is investigated using NMR spectroscopy, electrospray ionization mass spectrometry, and deuterium labeling, along with density functional theory calculations. These studies support an unusual catalytic mechanism in which an initial masked C-H bond activation initiates successive C-C bond cleavage events.