52178-65-1

Upstream product

• 600-00-0 ethyl 2-bromoisobutyrate 
• 100-52-7 benzaldehyde 
• 60-29-7 diethyl ether 
• 4303-71-3 triphenylmethyl sodium 
• 97-62-1 Ethyl isobutyrate 
• 25491-42-3 ethyl 2,2-dimethyl-3-oxo-3-phenylpropionate 
• 133817-05-7 ((1-ethoxy-2-methylprop-1-en-1-yl)oxy)triethylsilane 
• 31469-16-6 1-ethoxy-1-((trimethylsilyl)oxy)-2-methylpropene 
• 207446-12-6 2-dimethylsilanyl-2-methyl-propionic acid ethyl ester 
• 7664-93-9 sulfuric acid 
• 801301-34-8 2-dimethylstibanyl-2-methylpropionic acid ethyl ester 
• 934733-52-5 methyl 2-dimethylbismuthanyl-2-methylpropanoate 
• 7425-55-0 ethyl 2-iodo-2-methylpropanoate 
• 1265679-13-7 methyl 2-methyl-2-methyltellanylpropionate 

Downstream Products

• 100-52-7 benzaldehyde 
• 65-85-0 benzoic acid 
• 100-51-6 benzyl alcohol 
• 97-62-1 Ethyl isobutyrate 
• 23985-59-3 3-hydroxy-2,2-dimethyl-3-phenylpropanoic acid 
• 33950-46-8 1-phenyl-2,2-dimethyl-1,3-propanediol 
• 6335-78-0 ethyl isopropylidenephenylacetic carboxylate 
• 59697-90-4 3-Methyl-2-phenyl-3-butensaeure-ethylester 
• 20366-42-1 2.2-Dimethyl-3-phenyl-3-propionylamino-propionsaeure 
• 67437-31-4 1,1,3-Triphenyl-2,2-dimethyl-1,3-propandiol 
• 768-49-0 (2-methyl-1-propenyl)-benzene 
• 4412-08-2 3-methyl-2-phenylbut-2-enoic acid 
• 127852-67-9 (-)-(R)-3-hydroxy-2,2-dimethyl-3-phenylpropionic acid 
• 210910-12-6 (R)-(-)-1-phenyl-2,2,3-trimethylbutane-1,3-diol 

Relevant academic research and scientific papers

A Ball-Milling-Enabled Reformatsky Reaction

An operationally simple one-jar one-step mechanochemical Reformatsky reaction using in situ generated organozinc intermediates under neat grinding conditions has been developed. Notable features of this reaction protocol are that it requires no solvent, no inert gases, and no pre-activation of the bulk zinc source. The developed process is demonstrated to have good substrate scope (39–82 % yield) and is effective irrespective of the initial morphology of the zinc source.

1,4-Bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadienes as strong salt-free reductants for generating low-valent early transition metals with electron-donating ligands

Electron-rich organosilicon compounds, such as 1,4-bis(trimethylsilyl)-1,4- diaza-2,5-cyclohexadiene (2a), 2,5-dimethyl-1,4-bis(trimethylsilyl)-1,4-diaza-2, 5-cyclohexadiene (2b), 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-diaza-2, 5-cyclohexadiene (

Scope and mechanism of the electrochemical Reformatsky reaction of α-haloesters on a graphite powder cathode in aqueous anolyte

Six α-haloesters and eighteen carbonyl compounds were submitted to electrochemical coupling on a graphite powder cathode using aqueous anolyte free of organic solvents. Preparative yields of coupling products could be obtained with ethyl 2-bromoisobutyrate and aromatic aldehydes. Ethyl 2-bromopropionate was much less efficient. Extensive variation of applied potential, electrolyte composition, stoichiometry, catalyst, leaving halogen and activating substituents on the carbonyl compound led to the conclusion that the reaction mechanism in most cases proceeds via a radical intermediate generated from the halide reduction. Ethyl chloroacetate produced only trace amounts of coupling product, most probably by a carbanionic mechanism.

MNBA-mediated β-lactone formation: Mechanistic studies and application for the asymmetric total synthesis of tetrahydrolipstatin

Various β-lactones were prepared from β-hydroxycarboxylic acids by intramolecular dehydration condensation using MNBA, an effective coupling reagent, along with a nucleophilic catalyst. The transition state that provides the desired 4-membered ring model system is disclosed by density functional theory (DFT) calculations, and the structural features of the transition form are discussed. This method was successfully applied to the asymmetric total synthesis of tetrahydrolipstatin (THL), an antiobestic drug used in clinical treatment to inhibit the activity of pancreatic lipase.

Generation of carbanions through stibine-metal and bismuthine-metal exchange reactions and its applications to precision synthesis of ω-end-functionalized polymers

Generation of carbanions from organostibines and organobismuthines through heteroatom-metal exchange reactions was examined from synthetic and mechanistic viewpoints. The exchange reaction proceeded spontaneously upon treatment with various organometallic reagents, such as alkyl lithiums, tetraalkyl zincates, and alkyl magnesium halides to afford the corresponding carbanions quantitatively. Due to the high reactivity of these heteroatom compounds, the exchange reactions took place exclusively even in the presence of various polar functional groups, which potentially react with organometallic species. The advantage of this method was exemplified by the end-group transformation of living polymers that bear these heteroatom species at the ω-polymer end, prepared by using organostibine and bismuthine-mediated living radical polymerizations. Various polymers that bear polar functional groups and acidic hydrogen-for example, poly(methyl methacrylate), poly(butyl acrylate), poly(N-isopropyl acrylamide), and poly(2-hydroxyethyl methacrylate)-could be used in the exchange reactions, and subsequent trapping with electrophiles afforded the corresponding polymers with controlled molecular weights, molecular weight distributions, and end-group functionalities. Competition experiments showed that organostibines and organobismuthines were among the most reactive heteroatom compounds towards organometallic reagents and that their high reactivity was responsible for the high chemoselectivity in the exchange reaction. All's well that ends well: The generation of carbanions from organostibine and -bismuthine compounds was achieved thorough a heteroatom-metal exchange reaction (see scheme). The highly chemoselective exchange reaction could be applied to precision synthesis of varieties of ω-end- functionalized polymers that possess a polar functional group.

Highly enantioselective mukaiyama aldol reactions catalyzed by a chiral oxazaborolidinium ion: Total synthesis of (-)-inthomycin C

A cationic oxazaborolidinium-catalyzed asymmetric Mukaiyama aldol reaction of (1-methoxy-2-methyl-propenyloxy)-trimethylsilane with various aldehydes including α,β-disubstituted acroleins has been developed in high yields and enantioselectivities. The synthetic utility of this methodology was demonstrated in the first short synthesis of naturally occurring inthomycin C in high enantiopurity.

Enantioselective aldol reaction of silyl ketene acetals promoted by a Lewis base-activated Lewis acid catalyst

The enantioselective aldol reaction of a silyl ketene acetal was promoted by chiral phosphine oxide-activated tetrachlorosilane to afford the corresponding adduct in high yield with moderate enantioselectivity.

Lewis acid-aldehyde-solvent interactions. A computational approach for determining the critical amount of THF molecules necessary for achieving a high enantioselection in chiral oxazaborolidinone-promoted asymmetric aldol reactions

The effect of THF as a solvent on the enantioselectivity of oxazaborolidinone-promoted asymmetric aldol reactions of aldehydes with silylketene acetals was investigated. The use of 4-5 M equiv of THF, relative to the chiral borane, was required to achieve

Asymmetric hydrogenation of tert-alkyl ketones

A combined system of RuCl2(tolbinap)(pica) and an alkaline or organic phosphazene base catalyzes asymmetric hydrogenation of sterically congested tert-alkyl ketones (TolBINAP = 2,2-bis(di-4-tolylphosphino)-1,1-binaphthyl, PICA = α-picolylamine). Hydrogenation with RuH(η1-BH4)(tolbinap)(pica) does not require any strong base. Alcoholic solvents strongly affect the catalytic efficiency. The reaction proceeds smoothly in ethanol under 1-20 atm of H2 and at room temperature with a substrate to catalyst molar ratio of up to 100000. Various aliphatic, aromatic, heteroaromatic, and olefinic tert-alkyl ketones are convertible to the corresponding chiral carbinols in high enantiomeric purity. Olefinic and heteroaromatic functions are left intact. Certain cyclic ketones are also usable. The mode of enantioface selection is consistent and predictable. Copyright

Metal chloride-promoted aldol reaction of α-dimethylsilylesters with aldehydes, ketones, and α-enones

In the presence of a catalytic amount of LiCl, α-dimethylsilylesters (α-DMS-esters) 1 smoothly reacted with various aldehydes at 30°C to give aldols in good to high yields. On the other hand, the aldol reaction with ketones was effectively promoted by MgCl2 rather than by LiCl. α-Enones also underwent the metal chloride-promoted addition of 1 at the carbonyl carbon or β-carbon. Georg Thieme Verlag Stuttgart.