"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

doi:10.1021/om0104013

"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

Northwestern University

Research output: Contribution to journal › Article › peer-review

158 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 language	English
Pages (from-to)	283-292
Number of pages	10
Journal	Organometallics
Volume	21
Issue number	2
DOIs	https://doi.org/10.1021/om0104013
Publication status	Published - Feb 4 2002

ASJC Scopus subject areas

Inorganic Chemistry
Organic Chemistry

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"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 journal › Article › peer-review

Douglass, Michael R. ; Ogasawara, Masamichi ; Hong, Sukwon ; Metz, Matthew V. ; Marks, Tobin J. / "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. In: Organometallics. 2002 ; Vol. 21, No. 2. pp. 283-292.

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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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