We have established a method for the highly regio- and enantioselective functionalization of tert-butyl groups via intramolecular amide carbene insertion into C-H bonds, yielding γ-lactams with 91% ee in up to 99% yield. This reaction uses a ruthenium(II) phenyl oxazoline (Ru(II)-Pheox) complex. The catalytic intramolecular carbene transfer reaction to the primary C-H bond proceeds rapidly and selectively compared to that with secondary C-H, benzylic secondary C-H, tert-C-H, or sp2C-H bonds in the presence of 1 mol % Ru(II)-Pheox catalyst. This is the first example of a catalytic carbenoid insertion into an unactivated tert-butyl group with enantiocontrol at the carbenoid carbon.