Tetrahedron report number 234 Synthetic aspects of the use of organosilicon compounds under nucleophilic catalysis conditions

Fürin, G. G.; Vyazankina, O. A.; Gostevsky, B.A.; Vyazankin, N. S.

doi:10.1016/s0040-4020(88)90008-7

Cited by 119 publications

(28 citation statements)

References 314 publications

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“…that catalytic amounts of F − facilitate the intramolecular hydrosilylation of an azobenzene derivative . Alternatively, it seems likely that some of the required ligand exchange steps would be susceptible to nucleophilic catalysis …”

Section: Resultsmentioning

confidence: 99%

Hydrosilylation in Aryliminopyrrolide‐Substituted Silanes

Witteman

Evers

Zhan

et al. 2016

Chemistry A European J

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A range of silanes was synthesized by the reaction of HSiCl3 with iminopyrrole derivatives in the presence of NEt3 . In certain cases, intramolecular hydrosilylation converts the imine ligand into an amino substituent. This reaction is inhibited by factors such as electron-donating substitution on Si and steric bulk. The monosubstituted ((Dipp) IMP)SiHMeCl ((Dipp) IMP=2-[N-(2,6-diisopropylphenyl)iminomethyl]pyrrolide), is stable towards hydrosilylation, but slow hydrosilylation is observed for ((Dipp) IMP)SiHCl2 . Reaction of two equivalents of (Dipp) IMPH with HSiCl3 results in the hydrosilylation product ((Dipp) AMP)((Dipp) IMP)SiCl ((Dipp) AMP=2-[N-(2,6-diisopropylphenyl)aminomethylene]pyrrolide), but the trisubsitituted ((Dipp) IMP)3 SiH is stable. Monitoring the hydrosilylation reaction of ((Dipp) IMP)SiHCl2 reveals a reactive pathway involving ligand redistribution reactions to form the disubstituted ((Dipp) AMP)((Dipp) IMP)SiCl as an intermediate. The reaction is strongly accelerated in the presence of chloride anions.

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Section: Resultsmentioning

confidence: 99%

Hydrosilylation in Aryliminopyrrolide‐Substituted Silanes

Witteman

Evers

Zhan

et al. 2016

Chemistry A European J

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“…The earliest examples of Lewis base catalyzed reactions of the n-s* type were found in the chemistry of silanes. [198] The ability of silicon to attain stable, hypervalent states has long been known and has attracted a great deal of attention, especially in the context of studies on the stereochemical course of nucleophilic …”

Section: The N-s* Interaction: Lewis Base Catalysis With Polarized Anmentioning

confidence: 99%

“…Apart from the acceleration of the Michael addition of tin enolates by HMPA noted above, there are several reports of "uncatalyzed" Michael additions of silyl ketene acetals in highly dipolar aprotic solvents. In 1982, Tamura and coworkers reported the ability to effect the Michael addition of silyl ketene acetals to cyclic enones to form silyl enol ethers such as 198,199, and 157 by heating in acetonitrile at 55 8C for 2 h (Scheme 71). [258] Shortly thereafter, RajanBabu reported that similar additions proceeded even at room temperature in nitromethane.…”

Section: Neutral Lewis Basesmentioning

confidence: 99%

Lewis Base Catalysis in Organic Synthesis

2008

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The legacy of Gilbert Newton Lewis (1875-1946) pervades the lexicon of chemical bonding and reactivity. The power of his concept of donor-acceptor bonding is evident in the eponymous foundations of electron-pair acceptors (Lewis acids) and donors (Lewis bases). Lewis recognized that acids are not restricted to those substances that contain hydrogen (Brønsted acids), and helped overthrow the "modern cult of the proton". His discovery ushered in the use of Lewis acids as reagents and catalysts for organic reactions. However, in recent years, the recognition that Lewis bases can also serve in this capacity has grown enormously. Most importantly, it has become increasingly apparent that the behavior of Lewis bases as agents for promoting chemical reactions is not merely as an electronic complement of the cognate Lewis acids: in fact Lewis bases are capable of enhancing both the electrophilic and nucleophilic character of molecules to which they are bound. This diversity of behavior leads to a remarkable versatility for the catalysis of reactions by Lewis bases.

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“…Even so, the free fluoride ion is used widely in the syntheses of organofluoride derivatives; for example, compounds containing free fluorides are used as fluoridation agents [9]. Tetraalkylammonium fluoride has, in particular, been an important reagent in this field for many years, despite its disadvantages like decomposition upon drying [10,11]. Today, more selective and safer materials can be used, e.g., the commercially available “selectfluor” fluoridation agents comprised of diazobicyclo octane [12].…”

Section: Introductionmentioning

confidence: 99%

Simple One-Pot Syntheses and Characterizations of Free Fluoride- and Bifluoride-Containing Polymers Soluble in Non-Aqueous Solvents

et al. 2016

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One of the problems that arise with bifluoride- or fluoride-containing compounds is their poor solubility in non-aqueous solvents. We report herein a facile one-pot synthesis and the chemical analysis of fluoride/bifluoride-containing polymers, which are soluble in MeCN. Different polymers, such as Polyvinylacetate or Polyethylene imine and saccharides, such as maltodextrin, were complexed with ammonium (bi)fluoride using hydrogen bonds to form the desired (bi)fluoride-containing compounds. The newly formed hydrogen bonding (bi)fluoride-doped polymer matrices were analyzed using infrared and nuclear magnetic resonance spectroscopies, and X-ray diffraction. The promising materials also underwent impedance spectroscopy, conductivity measurements and preliminary tests as electrolytes for room temperature fluoride ion batteries along with an analysis of their performance.

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Tetrahedron report number 234 Synthetic aspects of the use of organosilicon compounds under nucleophilic catalysis conditions

Cited by 119 publications

References 314 publications

Hydrosilylation in Aryliminopyrrolide‐Substituted Silanes

Hydrosilylation in Aryliminopyrrolide‐Substituted Silanes

Lewis Base Catalysis in Organic Synthesis

Simple One-Pot Syntheses and Characterizations of Free Fluoride- and Bifluoride-Containing Polymers Soluble in Non-Aqueous Solvents

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