Intramolecular Edge-to-Face Aromatic π−π Interaction in Optically Active Ruthenium−Allenylidene Complexes for Enantioselective Propargylic Substitution Reactions

Novel optically active ruthenium−allenylidene complexes are prepared and characterized by X-ray crystallography. Intramolecular edge-to-face aromatic π−π interaction in the allenylidene complexes is observed between two phenyl groups in the allenylidene and chiral ligands, which may play a critical role in achieving the high enantioselectivity in the enantioselective propargylic substitution reactions of propargylic alcohols with nucleophiles.

本研究合成并通过X射线晶体衍射（X-ray crystallography）表征了新型光学活性钌-联烯亚基（allenylidene）配合物。研究观察到，该联烯亚基配合物中，联烯亚基配体与手性配体上的两个苯基之间存在分子内边对面芳香π-π相互作用；该相互作用或许在炔丙醇与亲核试剂参与的对映选择性炔丙基取代反应中，对实现高对映选择性起到关键作用。