* Jerome Waser, jerome.waser@epfl.ch, Laboratory of Catalysis and Organic Synthesis, Institute of Chemistry and Chemical Engineering, Ecole Polytechnique Federale de Lausanne, Ch-1015, Lausanne, Switzerland T. V. T. N. planned the research and performed the experiments, prepared the material for the redaction of the manuscript and the supporting information. A. B. performed preliminary studies on the [3+2] cycloaddition and participated to the investigation of the scope of the [3+2] cycloaddition. J. W. supervised the research, participated to the redaction and edition of the manuscript, as well as proof-read the supporting information. All authors have given approval to the final version of the manuscript.