"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

Michael R. Douglass, Masamichi Ogasawara, Sukwon Hong, Matthew V. Metz, Tobin Jay Marks*

*Corresponding author for this work

Research output: Contribution to journalArticle

158 Scopus citations

Abstract

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.

Original languageEnglish (US)
Pages (from-to)283-292
Number of pages10
JournalOrganometallics
Volume21
Issue number2
DOIs
StatePublished - Feb 4 2002

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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