Disclosed herein are compounds of the general Formula (I), and methods of synthesizing substituted bicyclo[1.1.1 jpentanes. The synthetic methods described herein use a [1.1.1]propellane, a Group VIII transition metal compound, a hydride source and a reagent that can contribute a substituent to form a substituted bicyclo[1.1.1]pentane, such as a compound of the general Formula (I).