Pentacoordinate silicon compounds: Stereochemical non-rigidity of chelates formed by intramolecular ring-closure. Crystal structure of 8-dimethylamino-1-trifluorosilylnaphthalene

Carré, Françis; Corriu, Robert J. P.; Kpoton, A.; Poirier, Monique; Royo, G.; Young, John C.; Belin, Claude

doi:10.1016/0022-328x(94)80147-9

Cited by 59 publications

(42 citation statements)

References 41 publications

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“…The presence of chiral carbon (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15) or silicon (16-21) atoms in molecules of pentacoordinate derivatives 1-21 leads to chemical non-equivalency of the NMR signals of the prochiral groups NCH 2 , SiMe 2 and CMe 2 . As a result, in the 1 H NMR spectra at room and lower temperatures the signals of NCH 2 protons appear as multiplets of ABsystem ( 2 J HH % 14-16 Hz) while the protons of SiMe 2 and CMe 2 groups appear as pairs of singlets.…”

Section: Enantiomer and Diastereomer Interconversionsmentioning

confidence: 99%

“…Stereodynamic processes in pentacoordinate silicon compounds; in particular the permutational isomerization of ligands, are the subject of intensive investigation [1][2][3][4]. These studies are important in increasing our understanding of mechanistic organosilicon chemistry, particularly for industrially important reactions such as the hydrolysis of halosilanes.…”

Section: Introductionmentioning

confidence: 99%

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Structures and stereochemical non-rigidity of Si-substituted N-(dimethylsilylmethyl)- and N-(methylphenylsilylmethyl)amides and -lactams

Negrebetsky

Taylor

Крамарова

et al. 2006

Journal of Organometallic Chemistry

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Section: Enantiomer and Diastereomer Interconversionsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Structures and stereochemical non-rigidity of Si-substituted N-(dimethylsilylmethyl)- and N-(methylphenylsilylmethyl)amides and -lactams

Negrebetsky

Taylor

Крамарова

et al. 2006

Journal of Organometallic Chemistry

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“…1-amino-8-trifluorosilylnaphthalene (2.318 ), [14] [15] as well as the dipyridine adduct of SiF 4 (1.932 ) [16] and the 2,2'-bipyridine adduct of SiF 4 (1.981 and 1.972 ). [17] The coordination geometry at the silicon atoms is almost trigonal bipyramidal.…”

Section: Preparationmentioning

confidence: 99%

(Dimethylaminomethyl)trifluorosilane, Me₂NCH₂SiF₃—A Model for the α‐Effect in Aminomethylsilanes

Mitzel

Vojinović

Foerster

et al. 2005

Chemistry A European J

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F3SiCH2NMe2 was prepared as a model for the investigation of the nature of the alpha-effect in alpha-aminosilanes, by fluorination of Cl3SiCH2NMe2 with SbF3. Under less mild conditions Si--C bond cleavage was also observed, leading to the double adduct F4Si(Me2NCH2SiF3)2, which was characterised by a crystal structure analysis showing that the central SiF4 unit is connected to Me2NCH2SiF3 via SiN dative bonds and FSi contacts. F3SiCH2NMe2 was characterised by multinuclear NMR spectroscopy (1H, 13C, 15N, 19F and 29Si), gas-phase IR spectroscopy and mass spectrometry. It is a dimer in the crystal (X-ray diffraction, crystal grown in situ), held together by two Si--N dative bonds. In solution and in the gas phase the compound is monomeric. The structure of the free molecule, determined by gas-phase electron diffraction, showed that, in contrast to former postulates, there are no attractive SiN interactions. Ab initio calculations have been carried out to explain the nature of the bonding. F3SiCH2NMe2 has an extremely flat bending potential for the Si-C-N angle; the high degree of charge transfer from the Si to the N atoms which occurs upon closing the Si-C-N angle is in the opposite direction to that expected for a dative bond. The topology of the electron density of F3SiCH2NMe2 was analysed. Solvent simulation calculations have shown virtually no structural dependence on the medium surrounding the molecule. The earlier postulate of Si-->N dative bonds in SiCN systems is discussed critically in light of the new results.

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“…[xlii] Interestingly, when subjected to the TBAF-promoted cross-coupling conditions in the presence of (Ph 3 P) 4 Pd and an aryl bromide, 79 shows only a modest reactivity. However, the reactivity can be greatly enhanced by treating 79 with boron trifluoride to convert it to trifluorosilane 80 in situ, [xliii] prior to adding (Ph 3 P) 4 Pd and the aryl bromide cross-coupling partner. Consequently, trans -disubstituted cyclopropanes 81 are isolated in good yields (Scheme 20).…”

Section: Sequential Cycloaddition/cross-couplingmentioning

confidence: 99%

Sequential Processes in Palladium‐Catalyzed Silicon‐Based Cross‐Coupling

Denmark

Liu

2010

Israel Journal of Chemistry

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Although developed somewhat later, silicon-based cross-coupling has become a viable alternative to the more conventional Suzuki-Miyaura, Stille-Kosugi-Migita, and Negishi cross-coupling reactions because of its broad substrate scope, high stability of silicon-containing reagents, and low toxicity of waste streams. An empowering and yet underappreciated feature unique to silicon-based cross-coupling is the wide range of sequential processes available. In these processes, simple precursors are first converted to complex silicon-containing cross-coupling substrates, and the subsequent silicon-based cross-coupling reaction affords an even more highly functionalized product in a stereoselective fashion. In so doing, structurally simple and inexpensive starting materials are quickly transformed into value-added and densely substituted products. Therefore, sequential processes are often useful in constructing the carbon backbones of natural products. In this review, studies of sequential processes involving silicon-based cross-coupling are discussed. Additionally, the total syntheses that utilize these sequential processes are also presented.

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Pentacoordinate silicon compounds: Stereochemical non-rigidity of chelates formed by intramolecular ring-closure. Crystal structure of 8-dimethylamino-1-trifluorosilylnaphthalene

Cited by 59 publications

References 41 publications

Structures and stereochemical non-rigidity of Si-substituted N-(dimethylsilylmethyl)- and N-(methylphenylsilylmethyl)amides and -lactams

Structures and stereochemical non-rigidity of Si-substituted N-(dimethylsilylmethyl)- and N-(methylphenylsilylmethyl)amides and -lactams

(Dimethylaminomethyl)trifluorosilane, Me₂NCH₂SiF₃—A Model for the α‐Effect in Aminomethylsilanes

Sequential Processes in Palladium‐Catalyzed Silicon‐Based Cross‐Coupling

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Pentacoordinate silicon compounds: Stereochemical non-rigidity of chelates formed by intramolecular ring-closure. Crystal structure of 8-dimethylamino-1-trifluorosilylnaphthalene

Cited by 59 publications

References 41 publications

Structures and stereochemical non-rigidity of Si-substituted N-(dimethylsilylmethyl)- and N-(methylphenylsilylmethyl)amides and -lactams

Structures and stereochemical non-rigidity of Si-substituted N-(dimethylsilylmethyl)- and N-(methylphenylsilylmethyl)amides and -lactams

(Dimethylaminomethyl)trifluorosilane, Me2NCH2SiF3—A Model for the α‐Effect in Aminomethylsilanes

Sequential Processes in Palladium‐Catalyzed Silicon‐Based Cross‐Coupling

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Product

Resources

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(Dimethylaminomethyl)trifluorosilane, Me₂NCH₂SiF₃—A Model for the α‐Effect in Aminomethylsilanes