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Usage

Uses

Used in Organic Synthesis:
N-Benzyltrimethylsilylamine is used as a reagent in organic synthesis for its ability to act as a nucleophile, facilitating a range of chemical reactions. Its reactivity is instrumental in the preparation of amines and amides, which are fundamental building blocks in the creation of complex organic molecules.
Used as a Protecting Group for Amines:
In the context of amine chemistry, N-Benzyltrimethylsilylamine serves as an effective protecting group. This role is crucial during the synthesis of complex organic compounds where the amine functionality needs to be temporarily masked to prevent unwanted side reactions, ensuring the selective formation of the desired product.
Used in Pharmaceutical Synthesis:
N-Benzyltrimethylsilylamine is utilized in the synthesis of pharmaceuticals, where its properties as a reagent and a protecting group are harnessed to facilitate the production of various medicinal compounds. Its versatility in organic synthesis makes it a valuable tool in the development of new drugs and the improvement of existing ones.
Used in the Formation of Amide Bonds:
N-BENZYLTRIMETHYLSILYLAMINE is also used in the formation of amide bonds, which are essential in the construction of peptide and protein structures. This application is particularly relevant in the fields of biochemistry and materials science, where the creation of novel bioactive molecules and polymers is of interest.

InChI:InChI=1/C10H17NSi/c1-12(2,3)11-9-10-7-5-4-6-8-10/h4-8,11H,9H2,1-3H3

Upstream product

• 999-97-3 1,1,1,3,3,3-hexamethyl-disilazane 
• 100-46-9 benzylamine 
• 75-77-4 chloro-trimethyl-silane 
• 1529-17-5 phenyltrimethylsilyl ether 
• 17599-61-0 N-benzylidene-1,1,1-trimethylsilanamine 
• 13435-12-6 N-Trimethylsilylacetamide 
• 3287-99-8 benzylamine hydrochloride 
• 24589-78-4 N-methyl-N-trimethylsilyl-2,2,2-trifluoroacetamide 

Downstream Products

• 39796-52-6 N-benzyl-2-aminoacetamide 
• 34582-41-7 2-[(benzylcarbamoyl)amino]acetic acid 
• 74963-37-4 N-benzyl-2-(methylamino)acetamide 
• 34582-46-2 2-(3-Benzyl-ureido)-propionic acid 
• 103676-09-1 2-amino-N-benzyl-3-phenylpropionamide 
• 100446-71-7 N-benzyl-4-(trimethylsiloxy)butanamide 
• 35046-48-1 (+/-)-1-phenyl-2-(benzylamino)ethanol hydrochloride 
• 588-46-5 N-(phenylmethyl)acetamide 
• 67-64-1 acetone 
• 18406-59-2 N-benzyl-N,N-bis(trimethylsilyl)amine 
• 103-67-3 benzyl-methyl-amine 
• 91579-00-9 2-Benzylamino-1-(2-chloro-phenyl)-ethanol; hydrochloride 
• 160885-24-5 (S)-3-Benzylamino-2-benzyloxycarbonylamino-propionic acid 
• 100-52-7 benzaldehyde 

Relevant academic research and scientific papers

Convergent Synthesis of Pyrrolidines, Piperidines, Perhydroazepines and Tetrahydroisoquinolines via Zirconocene η2-Imine Complexes

Zirconocene η2-imine complexes formed by a C-H activation route from a variety of amines are trapped by ω-halo-alkenes or -alkynes to afford 2,3-disubstituted pyrrolidines, piperidines and perhydroazepines on work up and cyclisation.In some cas

N-trimethylsilyl amines for controlled ring-opening polymerization of amino acid N-carboxyanhydrides and facile end group functionalization of polypeptides

We report a new strategy that uses N-trimethylsilyl (N-TMS) amine to mediate controlled ring-opening polymerization of amino acid N-carboxyanhydrides (NCAs). This polymerization proceeds via a unique, trimethylsilyl carbamate (TMS-CBM) propagating group t

Latent Nucleophilic Carbenes

Using DFT and ab initio calculations, we demonstrate that noncyclic formamidines can undergo thermal rearrangement into their isomeric aminocarbenes under rather mild conditions. We synthesized the silylformamidine, for which the lowest activation energy in this process was predicted. Experimental studies proved it to serve as a very reactive nucleophilic carbene. The reactions with acetylenes, benzenes, and trifluoromethane proceeded via insertion into sp, sp2, and spCH bonds. The carbene also reacted with the functional groups, such as CHO, COR, and CN at double or triple bonds, displaying high mobility of the trimethylsilyl group. The obtained silylformamidine can be considered as a latent nucleophilic carbene. It can be prepared in bulk quantities, stored, and used when the need arises. Calculation results predict similar behavior for some other silylated formamidines and related compounds.

Hypervalent Iodine(III) Reagents with Transferable Primary Amines: Structure and Reactivity on the Electrophilic α-Amination of Stabilized Enolates

A new family of hypervalent iodine reagents containing transferable primary amine groups is described. Benziodoxolone-based reagents were synthesized on the gram-scale through operationally simple reactions in up to quantitative yields. These bench-stable solids were characterized by X-ray analysis and successfully employed in the α-amination of indanone-based β-ketoesters in up to 83% yield. Mechanistic studies indicate a substitution mechanism involving an electrophilic amine.

Formation of Aromatic O-Silylcarbamates from Aminosilanes and Their Subsequent Thermal Decomposition with Formation of Isocyanates

A novel phosgene-free route to different isocyanates starts from CO2 and aminosilanes (cf. silylamines) to form so-called carbamoyloxysilanes (O-silylcarbamates), i. e., compounds with the general motif R1R2N?CO?O?SiR3R4R5 as potential precursors. We focused on the insertion reaction of CO2 into Si?N bonds of substrates with cyclic (mostly aromatic) amine substituents, i. e., PhNHSiMe3, (PhNH)2SiMe2, PhCH2NHSiMe3, p-(MeO)C6H4NHSiMe3, o-C6H4(NHSiMe3)2, 1,2-C6H10(NHSiMe3)2, o-C6H4(NHSiMe3)(CH2NHSiMe3) and 1,8-C10H6(NHSiMe3)2. Compared to previously investigated aminosilanes these reactions are hindered due to the reduced nucleophilicity/basicity of the N-atoms. Whereas slightly increased CO2 pressure (8 bar) and prolonged reaction times (24 h) were sufficient to overcome hindrance of the insertion into, e. g., PhNHSiMe3, intermolecular effects in some two-fold NHSiMe3 functionalized substrates led to partial mono-insertion (e. g., into o-C6H4(NHSiMe3)(CH2NHSiMe3)) or intra-molecular condensation of the intermediate insertion product in case of 1,8-C10H6(NHSiMe3)2 to form 1H-perimidin-2(3H)-one and other side products. Thermal treatment of mono-silylated O-silylcarbamates RHN?CO?O?SiR’3 resulted mainly in the formation of substituted ureas (RHN)2CO, whereas desired isocyanates could not be detected in these cases. Therefore, we continued our studies focussing on N,O-bissilylated precursors, which were obtained by an additional N-silylation of the O-silylated carbamates. This allowed the successful formation of isocyanates. As a sole byproduct hexamethyldisiloxane is formed. In all cases, known as well as yet unknown substances were characterised by 1H, 13C and 29Si NMR spectroscopy, along with X-ray diffraction analysis for crystallized solids.

Nickel-Catalyzed Decarbonylative Amination of Carboxylic Acid Esters

The reaction of carboxylic acid derivatives with amines to form amide bonds has been the most widely used transformation in organic synthesis over the past century. Its utility is driven by the broad availability of the starting materials as well as the kinetic and thermodynamic driving force for amide bond formation. As such, the invention of new reactions between carboxylic acid derivatives and amines that strategically deviate from amide bond formation remains both a challenge and an opportunity for synthetic chemists. This report describes the development of a nickel-catalyzed decarbonylative reaction that couples (hetero)aromatic esters with a broad scope of amines to form (hetero)aryl amine products. The successful realization of this transformation was predicated on strategic design of the cross-coupling partners (phenol esters and silyl amines) to preclude conventional reactivity that forms inert amide byproducts.

Zirconium Hydroaminoalkylation. An Alternative Disconnection for the Catalytic Synthesis of α-Arylated Primary Amines

Primary amine products have been prepared using zirconium-catalyzed hydroaminoalkylation of alkenes with N-silylated benzylamine substrates. Catalysis using commercially available Zr(NMe2)4 affords an alternative disconnection to acc

Sequential Barium-Catalysed N?H/H?Si Dehydrogenative Cross-Couplings: Cyclodisilazanes versus Linear Oligosilazanes

Starting from Ph3SiH, the barium precatalyst Ba[CH(SiMe3)2]2?(THF)3was used to produce the disilazane Ph3SiN(Bn)SiPh2NHBn (4) by sequential N?H/H?Si dehydrogenative couplings with BnNH2and Ph2SiH2. Substrate scope was extended to other amines and hydrosilanes. This smooth protocol gives quantitative yields and full chemoselectivity. Compound 4 and the intermediates Ph3SiNHBn and Ph3SiN(Bn)SiHPh2were structurally characterised. Further attempts at chain extension by dehydrocoupling of Ph2SiH2with 4 instead resulted in cyclisation of this compound, forming the cyclodisilazane c-(Ph2Si-NBn)2(5) which was crystallographically authenticated. The ring-closure mechanism leading to 5 upon release of C6H6was determined by complementary experimental and theoretical (DFT) investigations. Ba[CH(SiMe3)2]2?(THF)3and 4 react to afford the reactive Ba{N(Bn)SiPh2N(Bn)SiPh3}2, which was characterised in situ by NMR spectroscopy. Next, in a stepwise process, intramolecular nucleophilic attack of the metal-bound amide on the terminal silicon atom generates a five-coordinate silicate. It is followed by turnover-limiting β-C6H5transfer to barium; this releases 5 and forms a transient [Ba]?Ph species, which undergoes aminolysis to regenerate [Ba]?N(Bn)SiPh2N(Bn)SiPh3. DFT computations reveal that the irreversible production of 5 through such a stepwise ring-closure mechanism is much more kinetically facile (ΔG≠=26.2 kcal mol?1) than an alternative σ-metathesis pathway (ΔG≠=48.2 kcal mol?1).

Tridentate P,N,N-ligand promoted copper-catalyzed [3 + 2] cycloaddition of propargylic esters with β-enamino esters: Synthesis of highly functionalized pyrroles

A copper-catalyzed [3 + 2] cycloaddition of propargylic esters with β-enamino esters under mild reaction conditions for the construction of highly functionalized pyrroles has been developed. By employment of a newly developed tridentate P,N,N-ligand, a va

Imine hydrogenation by alkylaluminum catalysts

Di-isobutylaluminum hydride and tri-iso-butylaluminum (DIBAL 1, TIBAL 2) are shown to be efficient hydrogenation catalysts for a variety of imines at 100 °C and 100 atm of H2, operating via a hydroalumination/ hydrogenolysis mechanism.