Widening the roof: Synthesis and characterization of new chiral C1-symmetric octahydrofluorenyl organolanthanide catalysts and their implementation in the stereoselective cyclizations of aminoalkenes and phosphinoalkenes

被引：144

作者：

Douglass, Michael R. ^{[1
]}

Ogasawara, Masamichi ^{[1
]}

Hong, Sukwon ^{[1
]}

Metz, Matthew V. ^{[1
]}

Marks, Tobin J. ^{[1
]}

机构：

[1] Department of Chemistry, Northwestern University, Evanston, IL 60208-3113, United States

来源：

Organometallics | 2002年 / 21卷 / 02期

关键词：

Catalyst activity - Catalysts - Complexation - Crystallography - Molecular structure - Nuclear magnetic resonance spectroscopy - Recrystallization (metallurgy) - Synthesis (chemical);

D O I：

10.1021/om0104013

中图分类号：

学科分类号：

摘要：

New chiral C1-symmetric organolanthanide catalysts of the type Me2Si(OHF)(CpR*)LnN-(TMS)2 (OHF = η5-octahydrofluoreny]; Cp = η5-C5H3; R* = (-)-menthyl; Ln = Sm, Y, Lu; TMS = SiMe3) have been synthesized, characterized, and implemented in the enantioselective and diastereoselective cyclizations of aminoalkenes and phosphinoalkenes. Me2Si(OHF)(CpR*)LnCl2-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)-Me2Si(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.

引用

页码：283 / 292