Abstract
Two chiral C2‐symmetric diphenylphosphine dioxides bearing an original bis(triazolyl) backbone were prepared starting from inexpensive and readily available precursors. The key step involves the simultaneous formation of five bonds in one chemical step with 100 % atom efficiency through a copper‐catalyzed tandem [3+2] cycloaddition/dimerization reaction. Interestingly, these chiral inducers exhibited good to excellent catalytic activities as chiral Lewis base organocatalysts to promote useful stereoselective reactions.