16087-24-4

Usage

Structure

A benzene ring with a dimethylamino (N(CH3)2) group at the 1-position and a trimethylsilyl (Si(CH3)3) group at the 4-position

Physical State

Colorless liquid at room temperature

Odor

Mild

Usage

Reagent in organic synthesis, particularly in the formation of silicon-carbon bonds

Applications

Building block in the production of pharmaceuticals and agrochemicals, precursor in the preparation of functionalized silicon materials for industrial applications

Reactivity

Unique reactivity and ability to introduce silicon atoms into organic molecules

Safety

Handle with care, follow proper safety protocols for chemical handling and storage

InChI:InChI=1/C11H19NSi/c1-12(2)10-6-8-11(9-7-10)13(3,4)5/h6-9H,1-5H3

Upstream product

• 75-77-4 chloro-trimethyl-silane 
• 13190-50-6 4-dimethylaminophenyllithium 
• 586-77-6 4-bromo-N,N-dimethylaniline 
• 1450-14-2 1,1,1,2,2,2-hexamethyldisilane 
• 1197-19-9 4-cyano-N,N-dimethylaniline 
• 153014-93-8 FpSiMe₂C₆H₄-p-NMe₂ 
• 1112-54-5 vinyltriethylsilane 
• 698-70-4 4-Iodo-N,N-dimethylaniline 
• 121-69-7 N,N-dimethyl-aniline 
• 99-98-9 4-amino-N,N-dimethylaniline 

Downstream Products

• 18036-96-9 trimethyl-(4-trimethylsilanyl-phenyl)-ammonium; iodide 
• 121-69-7 N,N-dimethyl-aniline 
• 76-86-8 Triphenylsilyl chloride 
• 57650-42-7 tricarbonyl[5-(4-dimethylaminophenyl)cyclohexa-1,3-diene]iron 
• 1186026-67-4 1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-4-(trimethylsilyl)benzene 

Relevant academic research and scientific papers

Rh(I)-catalyzed silylation of aryl and alkenyl cyanides involving the cleavage of C-C and Si-Si bonds

The Rh(I)-catalyzed silylation of nitriles with disilanes is described. The cleavage of inert carbon-cyano and silicon-silicon bonds occurs in this catalysis. Copyright

Formation of silicon-carbon bonds by photochemical irradiation of (η5-C5H5)Fe(CO)2SiR3 and (η5-C5H5)Fe(CO)2Me to Obtain R3SiMe

Photochemical irradiation of an equimolar mixture of (η5 -C5H5)Fe(CO)2SiR3, FpSiR 3, and FpMe leads to the efficient formation of the silicon-carbon-coupled product R3SiMe, R3 = Me 3, Me2Ph, MePh2, Ph3, ClMe 2, Cl2Me, Cl3, Me2Ar (Ar = C 6H4-p-X, X = F, OMe, CF3, NMe2). Similar chemistry occurs with related germyl and stannyl complexes at slower rates, Si > Ge Sn. Substitution of an aryl hydrogen to form FpSiMe2C6H4-p-X has little effect on the rate of the reaction, whereas progressive substitution of methyl groups on silicon by Cl slows the process. Also, changing FpMe to FpCH2SiMe3 dramatically slows the reaction as does the use of (η5-C 5Me5)Fe(CO)2 derivatives. A mechanism involving the initial formation of the 16e intermediate (η5-C 5H5)Fe(CO)Me followed by oxidative addition of the Fe-Si bond accounts for the experimental results obtained.

Design, Synthesis, and Implementation of Sodium Silylsilanolates as Silyl Transfer Reagents

There is an increasing demand for facile delivery of silyl groups onto organic bioactive molecules. One of the common methods of silylation via a transition-metal-catalyzed coupling reaction employs hydrosilane, disilane, and silylborane as major silicon sources. However, the labile nature of the reagents or harsh reaction conditions sometimes render them inadequate for the purpose. Thus, a more versatile alternative source of silyl groups has been desired. We hereby report a design, synthesis, and implementation of storable sodium silylsilanolates that can be used for the silylation of aryl halides and pseudohalides in the presence of a palladium catalyst. The developed method allows a late-stage functionalization of polyfunctionalized compounds with a variety of silyl groups. Mechanistic studies indicate that (1) a nucleophilic silanolate attacks a palladium center to afford a silylsilanolate-coordinated arylpalladium intermediate and (2) a polymeric cluster of silanolate species assists in the intramolecular migration of silyl groups, which would promote an efficient transmetalation.

Generation of Aryllithium Reagents from N -Arylpyrroles Using Lithium

Treatment of 1-aryl-2,5-diphenylpyrroles with lithium powder in tetrahydrofuran at 0 °C results in the generation of the corresponding aryllithium reagents through reductive C-N bond cleavage.

P-Iodinations in hydrocarbon media: Continuous flow reactor application

Regiospecific iodination of aryl amines, that is, aryl compounds possessing strong electron donating groups (EDG's) in the p-position, is described. This procedure features not only the unique use of hydrocarbon media for such substitutions but also the absence of any oxidants aside from iodine itself. Further potential of this hydrocarbon media based electrophilic aromatic substitution is demonstrated by the coupling of the iodination with an in situ halogen/lithium exchange and product forming nucleophilic addition in a batch process. The protocol was ultimately scaled to a continuous flow reactor using an isolated p-iodoarylamine. Constituted as described, these procedures possess enhanced atom-economical, green and safety aspects compared to existing literature protocols.

Catalytic enantioselective arylation of glyoxylate with arylsilanes: Practical synthesis of optically active mandelic acid derivatives

Just a little does the trick! The catalytic enantioselective arylation using chiral dicationic palladium complexes provides a reliable and useful access to enantiomerically enriched mandelic-acid derivatives. Significantly low catalyst loading (down to 0.002 mol%) as well as easy catalyst handling are the advantage of this practical method.

Rhodium-catalyzed alkenylation of nitriles via silicon-assisted C-CN bond cleavage

Rhodium-catalyzed Mizoroki-Heck type reaction of nitriles via the cleavage of C-C bonds is described. Orthogonal and iterative functionalizations of arenes were also demonstrated by combining the present and conventional halide-based cross-coupling reacti

Rhodium-catalyzed silylation and intramolecular arylation of nitriles via the silicon-assisted cleavage of carbon-cyano bonds

A rhodium-catalyzed silylation reaction of carbon - cyano bonds using disilane has been developed. Under these catalytic conditions, carbon-cyano bonds in aryl, alkenyl, allyl, and benzyl cyanides bearing a variety of functional groups can be silylated. The observation of an enamine side product in the silylation of benzyl cyanides and related stoichiometric studies indicate that the carbon-cyano bond cleavage proceeds through the deinsertion of silyl isocyanide from η2-iminoacyl complex B. Knowledge gained from these studies has led to the development of a new intramolecular biaryl coupling reaction in which aryl cyanides and aryl chlorides are cross-coupled.

Kinetic Control in the Cleavage of Unsymmetrical Disilanes

A series of 12 phenyl-substituted arylpentamethyldisilanes 1a-1 have been synthesized in order to examine the regioselectivity of their nucleophilic Si,Si bond cleavage reactions under Still's conditions (MeLi/HMPA/0°C). It has been found that the sensitivity of these reactions to the electronic effects of the substituents in the phenyl ring could be described by the Hammett-type equation log(kA/kB) = 0.4334 + 2.421(Σσ); (correlation coefficient R = 0.983). The kA/kB ratio represents the relative rate of attack at silicon atom A (linked to the aryl ring) or at silicon atom B (away from the aryl ring) of the unsymmetrical disilanes. Thus, the present investigation shows that the earlier belief according to which the nucleophilic cleavage of unsymmetrical disilanes always produces the more stable silyl anionic species (thermodynamic control) should be abandoned, or at least seriously amended: kinetic factors appear to exert a primary influence on the regioselectivity of such reactions. Since the two major kinetic factors (i.e., electrophilic character of and steric hindrance at a given silicon atom) have opposite effects on the orientation of the reaction, it may happen that kinetic and thermodynamic control lead to the same result. For some of the unsymmetrical disilanes studied, the major reaction path was not the Si,Si bond cleavage; instead, Si-aryl bond breaking occurred, producing the corresponding aryl anions.