Figure also illustrates how various soluble C-H donors can be utilized in this protocol. The carbonylation of cycloalkanes with ring sizes ranging from five to eight carbons yielded good to excellent results (15-18, 57-93%). Similarly, linear alkanes can be successfully modified with an exclusive modification preference for secondary positions (19, 75%), despite the low difference in Bond Dissociation Energy (BDE) between secondary and primary hydrogens (BDE = 99 versus 101 kcal/mol). Notably, electron-withdrawing functional groups, such as ketones, can deactivate the alpha C-H bond in organic molecules due to a polarity mismatch with the electrophilic decatungstate photocatalyst. As a result, we can achieve excellent yield and selectivity (20, 85%) in the functionalization of the distal position of cyclopentanone.