The value of this synthetic method was further shown for the preparation of medicinallyrelevant compounds, such as homobenzylic ethers, aryl ethyl amines, and β-amino acids. Due to its practical and metal-free nature, we anticipate that this reaction will be of added value to those working in academia and industry. Additional studies to extend the application of this C(sp 3 )-C(sp 3 ) bond-forming strategy to new synthetic contexts are underway and will be reported in due course.