The reduction of amides and silyl esters with trichlorosilane-t-amines

Benkeser, Robert A.; Li, George S.; Mozdzen, Edward C.

doi:10.1016/s0022-328x(00)87858-4

Cited by 20 publications

(3 citation statements)

References 8 publications

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“…This oil was dissolved in 200 mL toluene and transferred to a flask fitted with a reflux condenser. Two hundred mmoles of trichlorosilane were added slowly through the reflux condenser, and the mixture was refluxed overnight [17]. After cooling to room temperature, the reaction was quenched by slowly pouring the reaction mixture into 200 g of crushed ice.…”

Section: -Hexylbenzyl Dimethylammonio Propane Sulfonate (C6bz)mentioning

confidence: 99%

Analysis of membrane proteins by two-dimensional electrophoresis: Comparison of the proteins extracted from normal orPlasmodium falciparum - infected erythrocyte ghosts

Rabilloud¹,

Blisnick²,

Heller³

et al. 1999

Electrophoresis

138

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Section: -Hexylbenzyl Dimethylammonio Propane Sulfonate (C6bz)mentioning

confidence: 99%

Analysis of membrane proteins by two-dimensional electrophoresis: Comparison of the proteins extracted from normal orPlasmodium falciparum - infected erythrocyte ghosts

Rabilloud¹,

Blisnick²,

Heller³

et al. 1999

Electrophoresis

138

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“…The only systematically investigated silanide-related systems for the preparation of organo(chloro)silanes currently remain the HSiCl 3 /NR 3 combination (“Benkeser reagent”; NR 3 = tertiary amine, typically N( n Pr) 3 or N( n Bu) 3 , in stoichiometric amounts) and the HSiCl 3 /[R 4 P]Cl pair ([R 4 P] + = quaternary phosphonium salt, typically [ n Bu 4 P] + , in catalytic amounts). The Benkeser reagent has been employed to produce organotrichlorosilanes through reductions of carboxyl or carbonyl derivatives, − hydrosilylations of alkenes or alkynes, − and the silylation of alkyl halides. , With respect to the latter transformation, it is important to note that nonactivated alkyl halides fail to yield the respective alkyl trichlorosilanes. Suitable substrates are benzyl and allyl halides as well as geminal polyhalogenated hydrocarbons.…”

Section: Introductionmentioning

confidence: 99%

Exhaustively Trichlorosilylated C₁ and C₂ Building Blocks: Beyond the Müller–Rochow Direct Process

Georg¹,

Teichmann²,

Bursch

et al. 2018

J. Am. Chem. Soc.

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The Cl-induced heterolysis of the Si-Si bond in SiCl generates an [SiCl] ion as reactive intermediate. When carried out in the presence of CCl or ClC═CCl (CHCl solutions, room temperature or below), the reaction furnishes the monocarbanion [C(SiCl)] ([A]; 92%) or the vicinal dianion [(ClSi)C-C(SiCl)] ([B]; 85%) in excellent yields. Starting from [B], the tetrasilylethane (ClSi)(H)C-C(H)(SiCl) (HB) and the tetrasilylethene (ClSi)C═C(SiCl) (B; 96%) are readily available through protonation (CFSOH) or oxidation (CuCl), respectively. Equimolar mixtures of HB/[B] or B/[B] quantitatively produce 2 equiv of the monoanion [HB] or the blue radical anion [B], respectively. Treatment of B with Cl ions in the presence of CuCl furnishes the disilylethyne ClSiC≡CSiCl (C; 80%); in the presence of [HMeN]Cl, the trisilylethene (ClSi)C═C(H)SiCl (D; 72%) is obtained. Alkyne C undergoes a [4+2]-cycloaddition reaction with 2,3-dimethyl-1,3-butadiene (CHCl, 50 °C, 3d) and thus provides access to 1,2-bis(trichlorosilyl)-4,5-dimethylbenzene (E1; 80%) after oxidation with DDQ. The corresponding 1,2-bis(trichlorosilyl)-3,4,5,6-tetraphenylbenzene (E2; 83%) was prepared from C and 2,3,4,5-tetraphenyl-2,4-cyclopentadien-1-one under CO extrusion at elevated temperatures (CHCl, 180 °C, 4 d). All closed-shell products were characterized by H,C{H}, and Si NMR spectroscopy; an EPR spectrum of [ nBuN][B] was recorded. The molecular structures of [ nBuN][A], [ nBuN][B], B, E1, and E2 were further confirmed by single-crystal X-ray diffraction. On the basis of detailed experimental investigations, augmented by quantum-chemical calculations, plausible reaction mechanisms for the formation of [A], [B], C, and D are postulated.

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“…17 Tertiary amides, both aromatic and aliphatic, are reduced by trichlorosilane with formation of ␣-aminotrichlorosilane products (Eqn [3]). 19 Rearrangement of N-trialkylsilylammonium ylides leads to ␣-amino-␣-cyanotrimethylsilanes. 20 The chemistry shown in Eqns [3] and [4] is limited to the preparation of tertiary amines.…”

Section: Introductionmentioning

confidence: 99%

?-Alkyl-?-aminosilanes: Synthesis via Alkylation and Hydrosilylation

Sieburth

Somers

O'Hare

et al. 1997

Appl. Organometal. Chem.

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The reduction of amides and silyl esters with trichlorosilane-t-amines

Cited by 20 publications

References 8 publications

Analysis of membrane proteins by two-dimensional electrophoresis: Comparison of the proteins extracted from normal orPlasmodium falciparum - infected erythrocyte ghosts

Analysis of membrane proteins by two-dimensional electrophoresis: Comparison of the proteins extracted from normal orPlasmodium falciparum - infected erythrocyte ghosts

Exhaustively Trichlorosilylated C₁ and C₂ Building Blocks: Beyond the Müller–Rochow Direct Process

?-Alkyl-?-aminosilanes: Synthesis via Alkylation and Hydrosilylation

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The reduction of amides and silyl esters with trichlorosilane-t-amines

Cited by 20 publications

References 8 publications

Analysis of membrane proteins by two-dimensional electrophoresis: Comparison of the proteins extracted from normal orPlasmodium falciparum - infected erythrocyte ghosts

Analysis of membrane proteins by two-dimensional electrophoresis: Comparison of the proteins extracted from normal orPlasmodium falciparum - infected erythrocyte ghosts

Exhaustively Trichlorosilylated C1 and C2 Building Blocks: Beyond the Müller–Rochow Direct Process

?-Alkyl-?-aminosilanes: Synthesis via Alkylation and Hydrosilylation

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Exhaustively Trichlorosilylated C₁ and C₂ Building Blocks: Beyond the Müller–Rochow Direct Process