Exploitation of Rh( i )–Rh( iii ) cycles in enantioselective C–C bond cleavages: access to β-tetralones and benzobicyclo[2.2.2]octanones

Rhodium(I)-catalyzed β-carbon eliminations of tert-cyclobutanols followed by oxidative addition give benzorhoda(III)cyclopentenes. These key intermediates trigger intramolecular C–H arylations leading to β-tetralones with quaternary stereogenic centers in excellent enantioselectivity. The versatility of the rhoda(III)cyclic species is further shown in formal intramolecular [4+2]-cycloadditions providing access to benzobicyclo[2.2.2]octanones.