17988-20-4

Usage

Uses

Used in Organic Synthesis:
(4-Methoxy-benzyl)-trimethyl-silane is used as a protecting group for reactive functional groups in organic synthesis. It temporarily masks these groups, preventing undesired reactions and allowing chemists to selectively modify other parts of the molecule.
Used in Chemical Reactions:
In the chemical reactions industry, (4-Methoxy-benzyl)-trimethyl-silane is used as a reagent to introduce the trimethylsilyl group onto different functional groups. This introduction expands the range of possible reactions and transformations that can be performed on the molecule, increasing the synthetic potential of the starting material.
Used in Pharmaceutical Industry:
(4-Methoxy-benzyl)-trimethyl-silane is used as a synthetic intermediate in the development of pharmaceutical compounds. Its ability to protect and modify functional groups makes it a valuable asset in the synthesis of complex organic molecules with potential therapeutic applications.
Used in Material Science:
In the material science field, (4-Methoxy-benzyl)-trimethyl-silane is employed in the synthesis of novel materials with specific properties. Its versatility in organic chemistry allows for the creation of materials with tailored characteristics for various applications, such as sensors, catalysts, or advanced materials for electronics and energy storage.

Upstream product

• 5076-68-6 diethyl 4-methoxyphenyl phosphate 
• 13170-43-9 (trimethylsilyl)methylmagnesium chloride 
• 103559-11-1 <4-chlorophenylthio(4-methoxyphenyl)methyl>trimethylsilane 
• 75748-09-3 (4-methoxybenzoyl)trimethylsilane 
• 83-33-0 inden-1-one 
• 98-86-2 acetophenone 
• 104-92-7 1-bromo-4-methoxy-benzene 
• 1822-00-0 trimethylsilylmethyllithium 
• 75-77-4 chloro-trimethyl-silane 
• 2746-25-0 p-Methoxybenzyl bromide 
• 38769-92-5 4-methoxybenzylmagnesium chloride 
• 18243-41-9 (bromomethyl)trimethylsilane 
• 623-12-1 4-chloromethoxybenzene 
• 82049-86-3 (trimethylsilyl)methylzinc chloride 

Downstream Products

• 123621-36-3 9-(4-Methoxy-benzyl)-9,10-dihydro-anthracene-9,10-dicarbonitrile 
• 101224-30-0 4-((trimethylsilyl)methyl)phenol 
• 2746-25-0 p-Methoxybenzyl bromide 
• 104-93-8 p-methylanizole 
• 104-21-2 p-methoxybenzyl acetate 
• 105-13-5 4-Methoxybenzyl alcohol 
• 18491-21-9 1-methoxy-4-(3-methylbut-3-en-1-yl)benzene 
• 100789-95-5 1-(4-methoxyphenyl)-4,4-dimethylpentan-3-one 
• 20574-98-5 4-(p-methoxyphenyl)but-1-ene 
• 123-11-5 4-methoxy-benzaldehyde 
• 886-30-6 (4-methoxy-benzyl)-succinic acid anhydride 
• 1657-55-2 1,2-bis(4-methoxyphenyl)ethane 
• 93578-03-1 2,3-bis-(4-methoxy-benzyl)-succinic acid-anhydride 
• 114378-10-8 [Bromo-(4-methoxy-phenyl)-methyl]-trimethyl-silane 

Relevant academic research and scientific papers

Nucleophile-assisted cleavage of benzyltrialkylsilane cation radicals

The cation radicals of benzyltrialkylsilanes have been generated using photoinduced electron transfer and characterized using transient absorption spectroscopy. Absolute rate constants for nucleophile-assisted C-Si bond cleavage have been determined, for different nucleophiles in different solvents and with different substituents on the phenyl ring. The short lifetime (-9 s) of the parent benzyltrimethylsilane cation radical in acetonitrile was unambiguously shown to be due to a rapid nucleophile-assisted bond cleavage, with the solvent acting as the nucleophile. Even in less polar solvents, such as dichloromethane, the lifetime of benzyltrimethylsilane cation radical is quite short (ca. 20 ns) unless trace amounts of water, which acts as an efficient nucleophile, are removed. Consistent with the nucleophile-assisted cleavage mechanism for the benzyltrialkylsilanes, sterically-demanding substituents on silicon decrease the rate constant for cleavage by as much as 4 orders of magnitude, depending upon the nucleophile. Similarly, increasing steric crowding on the nucleophile also decreases the rate constant, although smaller changes in the rate constants are observed. Electron-donating substituents (4-methyl and 4-methoxy) on the phenyl group also lead to a substantial decrease in the rate constant for cleavage of the cation radicals. When measurements are performed in the least nucleophilic solvent and under conditions that minimize contributions from adventitious nucleophiles, the lifetimes of the cation radicals of the benzyltrialkylsilanes can be so long that the rate of pseudofirst-order decay can not be accurately determined. If the cation radicals undergo unimolecular C-Si bond cleavage (i.e., not nucleophile-assisted) under these conditions, the rate constant for this process is estimated to be less than 104 s-1.

Visible-Light-Promoted Iron-Catalyzed C(sp2)–C(sp3) Kumada Cross-Coupling in Flow

A continuous-flow, visible-light-promoted method has been developed to overcome the limitations of iron-catalyzed Kumada–Corriu cross-coupling reactions. A variety of strongly electron rich aryl chlorides, previously hardly reactive, could be efficiently coupled with aliphatic Grignard reagents at room temperature in high yields and within a few minutes’ residence time, considerably enhancing the applicability of this iron-catalyzed reaction. The robustness of this protocol was demonstrated on a multigram scale, thus providing the potential for future pharmaceutical application.

Iron-catalyzed cross coupling of aryl chlorides with alkyl Grignard reagents: Synthetic scope and FeII/FeIV mechanism supported by x-ray absorption spectroscopy and density functional theory calculations

A combination of iron(III) fluoride and 1,3-bis(2,6-diiso-propylphenyl)imidazolin-2-ylidene (SIPr) catalyzes the high-yielding cross coupling of an electron-rich aryl chloride with an alkyl Grignard reagent, which cannot be attained using other iron catalysts. A variety of alkoxy-or amino-substituted aryl chlorides can be cross-coupled with various alkyl Grignard reagents regardless of the presence or absence of β-hydrogens in the alkyl group. A radical probe experiment using 1-(but-3-enyl)-2-chlorobenzene does not afford the corresponding cyclization product, therefore excluding the intermediacy of radical species. Solution-phase X-ray absorption spectroscopy (XAS) analysis, with the help of density functional theory (DFT) calculations, indicates the formation of a high-spin (S = 2) heteroleptic difluorido organoferrate(II), [MgX][FeIIF2(SIPr)-(Me/alkyl)], in the reaction mixture. DFT calculations also support a feasible reaction pathway, including the formation of a difluorido organoferrate(II) intermediate which undergoes a novel Lewis acid-assisted oxidative addition to form a neutral organoiron(IV) intermediate, which leads to an FeII/FeIV cata-lytic cycle, where the fluorido ligand and the magnesium ion play key roles.

Modular Functionalization of Arenes in a Triply Selective Sequence: Rapid C(sp2) and C(sp3) Coupling of C?Br, C?OTf, and C?Cl Bonds Enabled by a Single Palladium(I) Dimer

Full control over multiple competing coupling sites would enable straightforward access to densely functionalized compound libraries. Historically, the site selection in Pd0-catalyzed functionalizations of poly(pseudo)halogenated arenes has been unpredictable, being dependent on the employed catalyst, the reaction conditions, and the substrate itself. Building on our previous report of C?Br-selective functionalization in the presence of C?OTf and C?Cl bonds, we herein complete the sequence and demonstrate the first general arylations and alkylations of C?OTf bonds (in I dimer. This allowed the realization of the first general and triply selective sequential C?C coupling (in 2D and 3D space) of C?Br followed by C?OTf and then C?Cl bonds.

Direct oxidation of the C(sp2)-C(sp3) bond from benzyltrimethylsilanes to phenols

A novel pathway for direct conversion of benzylsilanes to phenols by oxidation with Na2S2O8 and oxygen is efficiently developed under mild and neutral conditions. The reaction shows good functional group tolerance to afford phenols in moderate yields. The possible mechanism is proposed based on the isotopic labeling trials.

Oxygen Activated, Palladium Nanoparticle Catalyzed, Ultrafast Cross-Coupling of Organolithium Reagents

The discovery of an ultrafast cross-coupling of alkyl- and aryllithium reagents with a range of aryl bromides is presented. The essential role of molecular oxygen to form the active palladium catalyst was established; palladium nanoparticles that are highly active in cross-coupling reactions with reaction times ranging from 5 s to 5 min are thus generated in situ. High selectivities were observed for a range of heterocycles and functional groups as well as for an expanded scope of organolithium reagents. The applicability of this method was showcased by the synthesis of the [11C]-labeled PET tracer celecoxib.

Palladium-catalyzed C(sp3)-C(sp2) cross-coupling of homoleptic rare-earth metal trialkyl complexes with aryl bromides: Efficient synthesis of functionalized benzyltrimethylsilanes

The first C(sp3)-C(sp2) cross-coupling of rare-earth metal alkyl complexes with aryl bromides has been developed. This reaction was conducted at low catalyst loading (0.5 mol%) and exhibited a broad substrate scope, thus providing a facile method for the synthesis of benzyltrimethylsilanes with diverse functional groups.

Palladium-catalyzed C(sp 3)-C(sp 2) cross-coupling of (trimethylsilyl)methyllithium with (hetero)aryl halides

The palladium-catalyzed direct cross-coupling of a range of organic chlorides and bromides with the bifunctional C(sp3)-(trimethylsilyl)methyllithium reagent is reported. The use of Pd-PEPPSI-IPent as the catalyst allows for the preparation of structurally diverse and synthetically versatile benzyl- and allylsilanes in high yields under mild conditions (room temperature) with short reaction times.

Iron fluoride/N-heterocyclic carbene catalyzed cross coupling between deactivated aryl chlorides and alkyl grignard reagents with or without β-hydrogens

High-yielding cross-coupling reactions of various combinations of aryl chlorides and alkyl Grignard reagents have been developed by using an iron(III) fluoride/1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene (SIPr) catalyst composite. The iron(III) fluoride/SIPr-catalyzed aryl-alkyl coupling demonstrates unprecedented scope for both aryl chlorides and alkyl Grignard reagents, thus enabling the first efficient coupling of electron-rich (deactivated) aryl chlorides with alkyl Grignard reagents without β-hydrogens. The present reaction is also effective for diverse alkyl Grignard reagents such as (trimethylsilyl)methyl, primary, and secondary alkyl Grignard reagents.

Direct catalytic cross-coupling of organolithium compounds

Catalytic carbon-carbon bond formation based on cross-coupling reactions plays a central role in the production of natural products, pharmaceuticals, agrochemicals and organic materials. Coupling reactions of a variety of organometallic reagents and organic halides have changed the face of modern synthetic chemistry. However, the high reactivity and poor selectivity of common organolithium reagents have largely prohibited their use as a viable partner in direct catalytic cross-coupling. Here we report that in the presence of a Pd-phosphine catalyst, a wide range of alkyl-, aryl- and heteroaryl-lithium reagents undergo selective cross-coupling with aryl- and alkenyl-bromides. The process proceeds quickly under mild conditions (room temperature) and avoids the notorious lithium halogen exchange and homocoupling. The preparation of key alkyl-, aryl- and heterobiaryl intermediates reported here highlights the potential of these cross-coupling reactions for medicinal chemistry and material science.