“Widening the Roof”: Synthesis and Characterization of New ChiralC1-Symmetric Octahydrofluorenyl Organolanthanide Catalysts and Their Implementation in the Stereoselective Cyclizations of Aminoalkenes and Phosphinoalkenes

New chiral C 1 -symmetric organolanthanide catalysts of the type Me 2 Si(OHF)(CpR*)LnN(TMS) 2 (OHF = η 5 -octahydrofluorenyl; Cp = η 5 -C 5 H 3; R* = (−)-menthyl; Ln = Sm, Y, Lu; TMS = SiMe 3 ) have been synthesized, characterized, and implemented in the enantioselective and diastereoselective cyclizations of aminoalkenes and phosphinoalkenes. Me 2 Si(OHF)(CpR*)LnCl 2 - Li(DME) 2 + catalyst precursors can be prepared in up to ∼90% diastereomeric purity and then converted into the corresponding amido catalysts, which can be isolated in ∼100% diastereomeric purity after recrystallization. The catalyst ( S )-Me 2 Si(OHF)(CpR*)YN(TMS) 2 has been crystallographically characterized. The activity of these catalysts for the hydroamination/cyclization of aminoalkenes and for the hydrophosphination/cyclization of phosphinoalkenes is described. Enantioselectivites as high as 67% are obtained in hydroamination, and diastereoselectivities of as high as 96% are obtained in hydrophosphination.