"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 J Marks

Research output: Contribution to journalArticle

157 Citations (Scopus)

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
Pages (from-to)283-292
Number of pages10
JournalOrganometallics
Volume21
Issue number2
DOIs
Publication statusPublished - Feb 4 2002

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ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

"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. / Douglass, Michael R.; Ogasawara, Masamichi; Hong, Sukwon; Metz, Matthew V.; Marks, Tobin J.

In: Organometallics, Vol. 21, No. 2, 04.02.2002, p. 283-292.

Research output: Contribution to journalArticle

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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.",
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