Active Metal Template Synthesis of Rotaxanes From BINOL‐Phosphate Macrocycles
Nikolai Brodt, Sophia Stadtfeld, Somayyeh Kheirjou, Tibor Schumski, Adrian M. Bialowons, Dennis Jansen, Felix Niemeyer, Torsten Schaller, Gebhard Haberhauer, Jan Riebe, Jochen NiemeyerABSTRACT
We demonstrate the use of macrocyclic BINOL‐phosphates for the active metal template synthesis of [2]rotaxanes via Cu(I)‐mediated alkyne‐azide cycloaddition. This novel methodology represents a key extension of the current active metal template approach beyond nitrogen‐based macrocycles and allowed for the synthesis of 17 differently functionalized chiral rotaxanes in yields up to 93%. Mechanistic studies combining DFT calculations, control experiments, and kinetic experiments support a dinuclear phosphate‐Cu 2 intermediate, which makes the formation of the rotaxanes kinetically competitive. Enabled by this novel methodology, we prepared both diastereomers of highly functionalized interlocked bis‐BINOL rotaxanes.