"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

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 Jay Marks^*

^*Corresponding author for this work

Chemistry

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

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

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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CCDC 178753: Experimental Crystal Structure Determination
Douglass, M. R. (Creator), Ogasawara, M. (Creator), Hong, S. (Creator), Metz, M. V. (Creator) & Marks, T. J. (Creator), Cambridge Crystallographic Data Centre, 2002
DOI: 10.5517/cc6007f, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc6007f&sid=DataCite
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@article{2d66014dbbfa4c8b85ddd0a4bcb89c17,

title = "{"}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",

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.",

author = "Douglass, {Michael R.} and Masamichi Ogasawara and Sukwon Hong and Metz, {Matthew V.} and Marks, {Tobin Jay}",

year = "2002",

month = feb,

day = "4",

doi = "10.1021/om0104013",

language = "English (US)",

volume = "21",

pages = "283--292",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "2",

}

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

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

TY - JOUR

T1 - "Widening the roof"

T2 - Synthesis and characterization of new chiral C1-symmetric octahydrofluorenyl organolanthanide catalysts and their implementation in the stereoselective cyclizations of aminoalkenes and phosphinoalkenes

AU - Douglass, Michael R.

AU - Ogasawara, Masamichi

AU - Hong, Sukwon

AU - Metz, Matthew V.

AU - Marks, Tobin Jay

PY - 2002/2/4

Y1 - 2002/2/4

N2 - 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.

AB - 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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