- Lithium and potassium bis(trimethylsilyl)amide: Utilizing non-nucleophilic bases as nitrogen sources
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Lithium and potassium bis(trimethylsilyl)amides are successfully utilized as nitrogen sources in palladium(0) catalyzed aminations of allylchloride.
- Bruening, Joerg
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- Anionic synthesis of primary amine functionalized polystyrenes via hydrosilation of allylamines with silyl hydride functionalized polystyrenes
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A general anionic ω-chain-end functionalization methodology is described and illustrated by the synthesis of ω-primary amine functionalized polystyrenes. First, the quantitative ω-silyl hydride functionalization of well-defined poly(styryl)lithium (Mn = 2200 and 14 100 g/mol) was effected with dimethylchlorosilane in hydrocarbon solution at room temperature. In the second step, involving amination by hydrosilation, the silyl hydride functionalized polystyrene was added quantitatively to 3-[N,N-bis(trimethylsilylamino]-1-propene, a protected amine, using Karstedt's Pt(0) hydrosilation catalyst in benzene. One of the principal advantages of this method is the fact that it is not necessary to use protecting groups for many functional groups, as illustrated by the quantitative primary amine functionalization of ω-silyl hydride functionalized poly(styryl)lithium with allylamine using the Karstedt's hydrosilation catalyst. The silyl hydride and amine functionalized polystyrenes were characterized by SEC, FTIR, 1H and 13C NMR, MALDI-TOF mass spectrometry, and end-group titration.
- Quirk, Roderic P.,Kim, Hoon,Polce, Michael J.,Wesdemiotis, Chrys
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- Synthesis of bifunctional disiloxanes: Via subsequent hydrosilylation of alkenes and alkynes
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The first protocol for the synthesis of unsymmetrical bifunctional 1,1,3,3-tetramethyldisiloxane derivatives via subsequent hydrosilylation of alkenes and alkynes is presented. The methodology described has vast functional group tolerance and is extremely efficient towards the formation of novel disiloxane-based building blocks.
- Szyling, Jakub,Januszewski, Rafa?,Jankowska, Kamila,Walkowiak, J?drzej,Kownacki, Ireneusz,Franczyk, Adrian
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supporting information
p. 4504 - 4507
(2021/05/17)
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- Preparation of N, N-bis(trimethylsilyl)allylamine
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The invention discloses a preparation method of N, N-bis(trimethylsilyl)allylamine, which comprises the following steps: 1. dropwisely adding an organic alkali solution into allyl bromide to carry outcondensation reaction, carrying out rotary evaporation to remove the organic solvent after the reaction is completed, and filtering to remove the generated metal salt, thereby obtaining a filtrate; and 2, adding deionized water into the filtrate, carrying out low-temperature water washing to remove metal salt and other water-soluble impurities, carrying out standing and liquid separation, separating out an organic phase, rectifying the organic phase, and collecting the N, N-bis(trimethylsilyl)allylamine finished product. The method has the advantages that 1, the reaction safety coefficient isgreatly improved, and the corrosion to equipment is effectively reduced; and 2, by-products or impurities generated in the preparation process are effectively removed, so that the purity and yield ofthe product are effectively improved.
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Paragraph 0019-0033
(2021/01/24)
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- METHOD FOR PRODUCING SILANE COMPOUND HAVING BIS-SILYLAMINO GROUP
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PROBLEM TO BE SOLVED: To provide a method for producing a silane compound having a bis-silylamino group efficiently, stably, and in good yield. SOLUTION: A method for producing a silane compound having a bis-silylamino group represented by the formula (3) includes reacting a compound represented by the formula (2): HSiR8nX3-n (2) with a compound represented by the formula (1) in the presence of a platinum compound where the compound represented by the formula (1) having a content of a compound represented by the formula (4) of not greater than 5.0 mass% is used. In the formulae, R1 is a C1-18 bivalent hydrocarbon group, R1' is a C3-20 bivalent hydrocarbon group, R2-R8 and R9 are each independently a substituted or unsubstituted C1-20 monovalent hydrocarbon group, X is a halogen or OR9, and n is an integer of 0-2. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0028
(2018/06/30)
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- [...] group-containing organosilicon compound
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[Problem] To provide a production method by which an organosilicon compound containing a bissilylamino group can be produced with high production efficiency and high yield through a simple and safe production process in which reaction control is easy. [Solution] A method for producing an organosilicon compound containing a bissilylamino group by subjecting an unsaturated hydrocarbon compound containing a bissilylamino group and an organosilicon compound containing a silicon-atom-bonded hydrogen atom to a hydrosilylation reaction in the presence of a hydrosilylation catalyst, the method being characterized in that the unsaturated hydrocarbon compound containing a bissilylamino group has a total content of a specific organosilicon compound and a specific amine compound of 0.2 mass% or less.
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Paragraph 0059
(2018/11/02)
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- Discovery of (S)-3′-hydroxyblebbistatin and (S)-3′-aminoblebbistatin: polar myosin II inhibitors with superior research tool properties
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In search of myosin II inhibitors with superior research tool properties, a chemical optimization campaign of the blebbistatin scaffold was conducted in this paper. (S)-Blebbistatin is the best known small-molecule inhibitor of myosin II ATPase activity. Unfortunately, as a research tool this compound has several deficiencies: it is photolabile and (photo)toxic, has low water solubility, and its (fluorescent) precipitates interfere in (fluorescence) readouts. In view of obtaining tool compounds with improved properties, both enantiomers of a series of D-ring modified polar analogs were prepared. We identified (S)-3′-hydroxyblebbistatin (S)-2 and (S)-3′-aminoblebbistatin (S)-3 as two myosin II inhibitors with a 30-fold higher water solubility than (S)-blebbistatin. These molecules furthermore do not cause interference in (fluorescence) readouts. (S)-2 and (S)-3 thus are superior alternatives to (S)-blebbistatin as research tools to study myosin II.
- Verhasselt, Sigrid,Roman, Bart I.,De Wever, Olivier,Van Hecke, Kristof,Van Deun, Rik,Bracke, Marc E.,Stevens, Christian V.
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supporting information
p. 2104 - 2118
(2017/03/11)
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- Synthesis of methyl(1-aminophosphonate)siloxane oligomers
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A synthesis of 1-aminophosphonate derivative of methylsiloxane oligomer was developed. A methodology of the introduction of 1-aminophosphonate fragment not only into the stable siloxane structures, but also into hydrolytically unstable alkoxyfunctional organosilicon compounds was suggested.
- Khairova,Milenin,Cherkaev,Stoikov,Muzafarov
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p. 1285 - 1288
(2017/02/05)
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- Reaction of hexylsilane with N-substituted allylamine and allyl chloride
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Reactions of allyldiethylamine and allylbis(trimethylsiyl)amine with hexylsilane are studied. The former reaction involves hydrogen evolution and Si-Si bond formation. The contribution of hydrosilylation is insignificant. Substituent exchange between the nitrogen and silicon atoms in the silane is found. In the reaction with allylbis(trimethylsilyl)amine, no evolution of hydrogen is observed, and hydrosilylation takes place. With allyl chloride, hydrosylilation, reduction, and Si-Si bond formation are observed. Quantumchemical calculations for the reactions with diethylallylamine and allylbis(trimethylsilyl)amine were carried out at the PM3, B3LYP/6-31G**, and B3LYP/LanL2DZ levels to show that these reactions all are thermodynamically allowed, and the difference in the behavior of the amines is explained by kinetic and conformational factors. Pleiades Publishing, Inc., 2006.
- Belyakova,Strozhenko,Chernyshev,Knyazev,Shutova,Shcherbakova
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p. 541 - 544
(2008/02/07)
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- Spin chemistry of organometallic compounds. 2. Interaction of N-bromohexamethyldisilazane with allyltriorganolsilanes
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Two instances have been considered demonstrating the influence of organoelement substituent on the reactivity of radicals generated from R3MCH2CH=CH2 (M = Si or Sn) in photoinduced interaction with (Me3Si)2
- Taraban, Marc B.,Kruppa, Alexander I.,Polyakov, Nikolai E.,Voronkov, Mikhail G.,Rakhlin, Vladimir I.,Grigor'ev, Stanislav V.,Volkova, Olga S.,Mirskov, Rudolph G.,Leshina, Tatyana V.
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p. 228 - 234
(2007/10/03)
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- Preparation of bis(3-aminopropyldimethylsilyl)benzene compounds
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1,2-, 1,3- or 1,4-bis(3-aminopropyldimethylsilyl)benzene is prepared by effecting hydrosilylation reaction between N,N-bis(trimethylsilyl)allylamine and 1,2-, 1,3- or 1,4-bis(dimethylsilyl)benzene in the presence of a platinum catalyst, followed by detrimethylsilylation reaction. The process is simple and inexpensive to synthesize the end compound in high yields without forming isomers.
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- Novel method for preparing bis(trimethylsilyl) amines via treatment with trimethylsilylamines and methyl iodide
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A convenient method for the synthesis of N,N-bis(trimethylsilyl)alkylamines has been reported. N-(Trimethylsilyl)diethylamine incorporated with a stoichiometric amount of methyl iodide was effective to convert primary amines, especially aromatic amines, and their monotrimethylsilyl derivatives into the corresponding N,N-bis(trimethylsilyl)amine derivatives in high yields. In the case of N-trimethylsilyl derivatives of aliphatic primary amines, a half-amount of silylamines served as a silylation agent against another half-amount of silylamines in the presence of 0.5 equivalent of methyl iodide to give N,N-bis(trimethylsilyl)alkylamines in good yield. Allyl iodide, allyl bromide and benzyl bromide were also effective to promote the silylation activity of silylamines.
- Hamada, Yoshitaka,Yamamoto, Yasushi,Shimizu, Hideaki
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- Aminosilanes in organic synthesis. Hydrostannation of N,N-bis(trimethylsilyl)propargylamine. Facile and selective routes to (E)-allylic amines
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The addition of tributyl tin hydride to N,N-bis(trimethylsilyl)propargylamine yielded E-1-tributylstannyl-3-prop-1-ene 2 in 90percent yield and 96percent stereochemical purity.The functional vinyl tin reagent 2 was shown to give short and selective access to primary allylic amines.The reactions of 2 with aryl and vinyl bromides in the presence of a palladium catalyst gave substituted E-allylic amines in high yields.The reaction of 2 with butyl lithium yielded E-γ-vinyl lithium from which selective access to E-allylic amines was obtained.Key words: silylamines / propargylamines / hydrostannation / vinyl tin / vinyl lithium / (E)-allylamines
- Corriu, R.J.P.,Bolin, G.,Moreau, J.J.E.
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p. 273 - 280
(2007/10/02)
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- CONTRIBUTIONS TO THE CHEMISTRY OF ORGANIC SILICON-NITROGEN-COMPOUNDS, I. SYNTHESIS OF N,N-BIS-(TRIMETHYLSILYL)AMINES
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The preparation of N,N-bis-(trimethylsilyl)amines 1 has been investigated.Three convenient methods are reported: A, Transfer of (catalytically) activated Tms-groups to amines starting from N-silylated carbonamides, B, silylation of amines with trimethylsilylchloride 5/NEt3 in the presence of TiCl4, C, silylation of primary amines 4 or mono-(trimethylsilyl)amines 16 with CF3SO3 Tms/NEt3 or TmsI/NEt3.Methods A and B are limited to the silylation of (ar)alkylamines which have no branched α-position. Key words: N,N-bis-(trimethylsilyl)amines; N,N-bis-silylamines; N-silylcarbonamides.
- Schorr, Manfred,Schmitt, Wilfried
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- An Efficient Route to GABA-Analogous Amino Acids: Cyclopropanation of N-Silylated Allylamines and Enamines
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N-Silylated allylamines 1 are effectively transformed into methyl cyclopropanecarboxylates 2 by methyl diazoacetate under Rh2(OAc)4 catalysis.Derivatives 2a and 2b are smoothly converted into trans-substituted amino acids 6a and 6b, respectively, and to bicyclic γ-lactams 5a and 5b.The pharmacologically interesting γ-aminobutyric acid (GABA) analogue trans-6a is now available in few steps.Photochemical and thermal Fe(CO)5-induced hydrogen shift converts allylamine derivatives 1 into N-silylated enamines 7.While enamine (E)-7a can be cyclopropanated with methyl diazoacetate under Cu(acac)2 catalysis to afford the desired cyclopropane derivatives 8a in good yield, the other enamines are rather unreactive towards the carbenoid.Use of an optically active catalyst provides 8a with an ee of 56percent (cis) and 20percent (trans).Acid induced ring cleavage of 8a gives the β-formyl ester 10a, and reduction of 8a followed by desilylation provides the aminocyclopropane 14 in good overall yield, thus demonstrating that cyclopropanes like 8a can serve as useful synthetic intermediates. --- Key Words: Amino acids / GABA analogues / Aminocyclopropanes / Enamines, N-silylated / Cycloaddition
- Paulini, Klaus,Reissig, Hans-Ulrich
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p. 455 - 461
(2007/10/02)
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- A simple synthesis of primary E-allylic amines from 1-tributylstannyl-3-bis(trimethylsilyl)amino prop-1-ene
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A facile and selective preparation of primary E-allylic amines is described from the readily available γ-amino vinylic tin reagent 2, either by using the direct palladium catalysed coupling of the vinyl tin moitie or via conversion to a γ-amino vinyl lithium reagent.
- Corriu,Bolin,Moreau
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p. 4121 - 4124
(2007/10/02)
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- Amination Reaction of Allylic Chlorides with Silver Iodide/Lithium N,N-Disilylamide Mixed Reagents
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The nucleophilic substitution of allylic chlorides with silver iodide/lithium N,N-disilylamide mixed reagents gives protected primary amines in good to excellent yields.
- Murai, Toshiaki,Yamamoto, Mikio,Kato, Shinzi
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p. 789 - 790
(2007/10/02)
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- A Simple Synthesis pf Primary Amines via their N,N-Bis(trimethylsilyl) Derivatives
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Primary halogen compounds 1 or the corresponding tosylates react with sodium bis(trimethylsilyl)amide (2) in hexamethyldisilazane to form N,N-bis(trimethylsilyl)amines 3, which are converted into the amine hydrochlorides 5 by treatment with aqueous HCl.
- Bestmann, Hans Juergen,Woelfel, Gerhard
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p. 1250 - 1254
(2007/10/02)
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- Synthesis and Properties of Na3-C3H5Fe(NO)(CO)CN> and η3-C3H5Fe(NO)(CO)CNMe (η3-C3H5 = Allyl)
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The allyl iron complexes η3-C3H5Fe(NO)(CO)L (L = CN(-), CNMe) can be obtained by the reaction of η3-C3H5Fe(NO)(CO)2 with NaN(SiMe3)2 and subsequent methylation. - Keywords: Allyl Nitrosyl Carbonyl, Cyano, Isonitrile Iron Complexes
- Moll, Matthias,Behrens, Helmut,Seibold, Hans-Juergen,Merbach, Peter
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p. 409 - 410
(2007/10/02)
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