31469-15-5

Usage

Uses

Used in Organic Synthesis:
DIMETHYLKETENE METHYL TRIMETHYLSILYL ACETAL is used as a functional equivalent of enolate of methyl isobutyrate in various electrophilic reactions, such as alkylation, aldol reaction, and Michael reaction. It serves as an ester enolate surrogate, enabling the formation of carbon-carbon bonds and the synthesis of complex organic molecules.
Used in Polymer Synthesis:
DIMETHYLKETENE METHYL TRIMETHYLSILYL ACETAL is used as an initiator for group-transfer polymerization of acrylates. It facilitates the controlled polymerization process, leading to the formation of polymers with specific properties and structures.
Used in Conjugate Addition and Aldol Reactions:
DIMETHYLKETENE METHYL TRIMETHYLSILYL ACETAL is used as a versatile reagent in conjugate addition and aldol reactions, enabling the formation of carbonyl compounds and the synthesis of various organic compounds.
Used in the Synthesis of Chiral β-Lactams:
DIMETHYLKETENE METHYL TRIMETHYLSILYL ACETAL is used in the synthesis of chiral β-lactams by reacting with (S)-alkylidene(1-arylethyl)amines in the presence of titanium tetrachloride. It acts as a catalyst or initiator in this reaction, enabling the formation of biologically active compounds.
Used in Nitroarylation, Oxidation, Dimerization, and Cycloadditions:
DIMETHYLKETENE METHYL TRIMETHYLSILYL ACETAL is used as a reagent in various other organic reactions, such as nitroarylation, oxidation, dimerization, and cycloadditions. It contributes to the formation of diverse organic compounds and the development of novel synthetic routes.

Preparation

The title compound is a prototypical ketene silyl acetal (KSA) that can been prepared by either of the two most commonly employed methods: (a) deprotonation of the α-hydrogen of an ester followed by silylation (1),16 and (b) metal-catalyzed hydrosilylation of α,β-unsaturated esters(2).

Purification Methods

Add Et2O, wash with cold H2O, dry (Na2SO4), filter, evaporate Et2O, and distil the oily residue in a vacuum. [Ainsworth et al. J Organometal Chem 46 59 1972.]

InChI:InChI=1/C8H18O2Si/c1-7(2)8(9-3)10-11(4,5)6/h1-6H3

Upstream product

• 75-77-4 chloro-trimethyl-silane 
• 547-63-7 Methyl isobutyrate 
• 6065-54-9 dimethyl dimethylmalonate 
• 23426-63-3 2-bromo-2-methylpropionic acid methyl ester 
• 22421-97-2 methyl 2-chloroisobutyrate 
• 27607-77-8 trimethylsilyl trifluoromethanesulfonate 
• 993-07-7 trimethylsilan 
• 80-62-6 methacrylic acid methyl ester 
• 67-64-1 acetone 
• 187809-34-3 C₅H₁₀O₂ 
• 18162-48-6 tert-butyldimethylsilyl chloride 

Downstream Products

• 68234-97-9 2-(1-Adamantyl)-2-methylpropionsaeure-methylester 
• 58649-09-5 methyl 2-methyl-2-(3-oxocyclohexyl)propanoate 
• 61866-20-4 methyl 3-hydroxy-2,2-dimethyl-3-phenylpropanoate 
• 92157-35-2 methyl 3-hydroxy-3-(4-methoxyphenyl)-2,2-dimethylpropionate 
• 58649-05-1 methyl 2,2-dimethyl-5-oxo-3,5-diphenylpentanoate 
• 75436-65-6 methyl 2-methyl-2-(2-oxocyclohexyl)propionate 
• 57956-46-4 methyl (4E)-2,2-dimethyl-5-phenyl-3-trimethylsilyloxypentanoate 
• 57956-40-8 methyl 3-hydroxy-2,2-dimethyl-5-phenylpentanoate 
• 79388-25-3 methyl 2,2-dimethyl-3-(phenylamino)-3-(2-pyridyl)propanoate 
• 79388-23-1 methyl 3-(furan-2-yl)-2,2-dimethyl-3-(phenylamino)propanoate 
• 79388-24-2 methyl 2,2-dimethyl-3-(N-phenylamino)-3-(2-thienyl)propionate 
• 86426-00-8 methyl 3-hydroxy-2,2-dimethyl-3,3-diphenylpropanoate 
• 88222-69-9 2-Methyl-2-(2,3,5-tri-O-benzyl-β-D-ribofuranosyl)propionsaeure-methylester 
• 88222-68-8 2-Methyl-2-(2,3,5-tri-O-benzyl-α-D-ribofuranosyl)propionsaeure-methylester 

Relevant academic research and scientific papers

Addition of ketene silyl acetals to the triplet excited state of C60 via photoinduced electron transfer leading to the fullereneacetates

The photochemical carbon-carbon bond formation of C60 with ketene silyl acetals is described to give a new way for fullerene functionalization chemistry. The photoaddition of ketene silyl acetals to C60 occurs efficiently under irradiation of the visible light in benzene as well as benzonitrile to yield the fullereneacetates. The comparison of the observed rate constants determined from the dependence of the quantum yields on the concentrations of ketene silyl acetals as well as the quenching of triplet excited state of C60 by ketene silyl acetals with those predicted for the electron transfer processes indicates that the photoaddition proceeds via photoinduced electron transfer from ketene silyl acetals to the triplet excited state of C60. The negative shift in the one-electron reduction potentials by the adduct formation of C60 is examined by the cyclic voltammetry measurements. The factors to control the formation of mono- and bisadducts of C60 are clarified based on the rates of photoinduced electron transfer from ketene silyl acetals to the triplet excited states of C60 and the adducts.

A Disulfonimide Catalyst for Highly Enantioselective Mukaiyama-Mannich Reaction

A new BINOL-derived chiral disulfonimide has been developed by introducing 4-methyl-3,5-dinitrophenyl substituents at its 3- and 3′-positions. This chiral disulfonimide catalyst displays high catalytic efficacy toward the asymmetric Mukaiyama-Mannich reac

Chiral Modification of the Tetrakis(pentafluorophenyl)borate Anion with Myrtanyl Groups

The synthesis and characterization of chiral [B(C6F5)4]– derivatives bearing a myrtanyl group instead of a fluoro substituent in the para position are described. These new chiral borates were isolated as their bench-stable lithium, sodium, and cesium salts. The corresponding trityl salts were prepared and tested as catalysts in representative counteranion-directed Diels–Alder reactions and Mukaiyama aldol additions but no enantioselectivity was obtained. Preformation of a chalcone-derived silylcarboxonium ion with the chiral borate as counteranion did not lead to any asymmetric induction in a reaction with cyclohexa-1,3-diene.

Preparation method of fexofenadine

The invention provides a preparation method of fexofenadine, which comprises the following steps: by using bromobenzene as a raw material, carrying out Friedel-Crafts acylation reaction to obtain 4'-bromo-4-chlorophenone ; enabling 4'-bromo-4-chlorobutanone and 1-methoxy-1-(trimethylsiloxy)-2-methyl-1-propene to subjected to coupling reaction to obtain 2-[4-(4 -chloro-1-butyryl)phenyl]-2-methyl methyl propionate; and sequentially carrying out N-alkylation, carbonyl reduction and alkaline hydrolysis on 2-[4-(4 -chloro-1-butyryl)phenyl]-2-methylpropanoate to obtain fexofenadine. The method has the advantages of cheap and easily available raw materials, easiness in operation, high yield, low cost, no meta-isomer, suitability for industrial production and the like.

Silanediol versus chlorosilanol: Hydrolyses and hydrogen-bonding catalyses with fenchole-based silanes

Biphenyl-2,2’-bisfenchyloxydichlorosilane (7, BIFOXSiCl2) is synthesized and employed as precursor for the new silanols biphenyl-2,2’-bisfenchyloxychlorosilanol (8, BIFOXSiCl(OH)) and biphenyl-2,2’-bisfenchyloxysilanediol (9, BIFOXSi(OH)2

Asymmetric Total Synthesis of (-)-(3 R)-Inthomycin C

A short (10 step) and efficient (15% overall yield) synthesis of the natural product (-)-(3R)-inthomycin C is reported. The key steps comprise three C-C bond-forming reactions: (i) a vinylogous Mukaiyama aldol, (ii) an olefin cross-metathesis reaction, and (iii) an asymmetric Mukaiyama-Kiyooka aldol. This route is notable for its brevity and has the advantage of lacking stoichiometric tin-promoted cross-coupling reactions present in previous approaches. Initial investigations on the biological activity of (-)-(3R)-inthomycin C and structural analogues on human cancer cell lines are also described for the first time.

The Catalytic Asymmetric Mukaiyama–Michael Reaction of Silyl Ketene Acetals with α,β-Unsaturated Methyl Esters

α,β-Unsaturated esters are readily available but challenging substrates to activate in asymmetric catalysis. We now describe an efficient, general, and highly enantioselective Mukaiyama–Michael reaction of silyl ketene acetals with α,β-unsaturated methyl esters that is catalyzed by a silylium imidodiphosphorimidate (IDPi) Lewis acid.

Eosin Y- and Copper-Catalyzed Dark Reaction to Construct Ene-γ-Lactams

Eosin Y, a common organo-photocatalyst in visible-light photoredox processes, was found to show excellent catalytic activities for thermal redox reactions under a catalytic amount of Cu(OAc)2. With this catalytic system, vinyl azides and ketene silyl acetals combine to form formal [3 + 2] cycloadducts by α-ester radical addition without light irradiation. This method provides a mild and straightforward paradigm to prepare important synthons of five-membered ene-γ-lactams and bridge ring lactams. It is the first example of an eosin Y-catalyzed redox reaction in the dark.

Synthesis of Conformationally Constrained Esters and Amines by Pd-Catalyzed α-Arylation of Hindered Substrates

The α-arylation of sterically hindered silyl ketene acetals (SKAs) with sterically hindered aryl bromides occurs efficiently using Pd[P(t-Bu)3]2 as the optimal catalyst and ZnF2 as a promoter. Less sensitive P(t-Bu)3

Pestalotiopsin A. Enantioselective construction of potential building blocks derived from antipodal cyclobutanol intermediates

(Chemical Equation Presented) D-Glyceraldehyde acetonide has been used as the starting point for accessing the enantiomeric cyclobutanols 11 in optically pure condition. The dextrorotatory enantiomer has been transformed in five steps into the [3.2.0] bic