A review. The catalytic activation of C-C bonds bears significant ecol. and economical advantages. In this account, the authors describe their results for an enantioselective C-C activation of sym. substituted tert-cyclobutanols. Subsequent downstream reactions of the obtained alkylrhodium intermediate give rise to a wide range of synthetically versatile products bearing all-carbon quaternary stereogenic centers with excellent enantioselectivities.