21160-26-9

Upstream product

• 67-56-1 methanol 
• 6832-17-3 2-diazo-1-(4-methoxyphenyl)ethanone 
• 1738-36-9 2-methoxyacetonitrile 
• 13139-86-1 4-methoxyphenyl magnesium bromide 
• 55991-65-6 [1-(4-methoxyphenyl)vinyloxy]trimethylsilane 
• 4009-98-7 (methoxymethyl)triphenylphosphonium chloride 
• 874-90-8 4-methoxybenzonitrile 
• 100-06-1 1-(4-methoxyphenyl)ethanone 
• 1280738-17-1 triisopropyl((1-(4-methoxyphenyl)vinyl)oxy)silane 
• 52898-49-4 4,N-dimethoxy-N-methylbenzamide 
• 107-30-2 chloromethyl methyl ether 
• 1638623-54-7 methoxy((1-(4-methoxyphenyl)vinyl)oxy)dimethylsilane 
• 124-41-4 sodium methylate 
• 2196-99-8 2-chloro-1-(4-methoxyphenyl)ethanone 

Downstream Products

• 38493-07-1 3-methoxy-2-(4-methoxy-phenyl)-chromenylium; chloride 
• 108977-45-3 5-methoxy-4,6-bis-(4-methoxy-phenyl)-pyran-2-one 
• 108368-41-8 5-methoxy-6-(4-methoxy-phenyl)-4-phenyl-pyran-2-one 
• 61821-26-9 2-Methoxy-1,3-bis-(4-methoxy-phenyl)-propane-1,3-dione 
• 61416-33-9 C₁₆H₁₅ClN₂O₃ 
• 61416-31-7 C₂₃H₂₂N₂O₅S 
• 99186-45-5 2-(4-methoxy-1-phenyl)ethyl formate 
• 147159-76-0 2-methoxy-1-(4-methoxyphenyl)ethan-1-ol 
• 59931-67-8 6-(4-methoxyphenyl)-3,4-diphenyl-α-pyrone 
• 1402458-65-4 (+)-3-methoxy-2-(4-methoxyphenyl)-2-trimethylsilyloxypropanenitrile 

Relevant academic research and scientific papers

Intermolecular C-O Bond Formation with Alkoxyl Radicals: Photoredox-Catalyzed α-Alkoxylation of Carbonyl Compounds

Due to the high reactivity of alkoxyl (RO·) radicals and their propensity to easily undergo β-scission or Hydrogen Atom Transfer (HAT) reactions, intermolecular alkoxylations involving RO· radicals are barely described. We report herein for the first time the efficient intermolecular trapping of alkoxyl radicals by silyl enol ethers. This photoredox-mediated protocol enables the introduction of both structurally simple and more complex alkoxy groups into a wide range of ketones and amides.

Continuous Flow Acylation of (Hetero)aryllithiums with Polyfunctional N,N-Dimethylamides and Tetramethylurea in Toluene

The continuous flow reaction of various aryl or heteroaryl bromides in toluene in the presence of THF (1.0 equiv) with sec-BuLi (1.1 equiv) provided at 25 °C within 40 sec the corresponding aryllithiums which were acylated with various functionalized N,N-

Tandem Acid/Pd-Catalyzed Reductive Rearrangement of Glycol Derivatives

Herein, we describe the acid/Pd-tandem-catalyzed transformation of glycol derivatives into terminal formic esters. Mechanistic investigations show that the substrate undergoes rearrangement to an aldehyde under [1,2] hydrogen migration and cleavage of an oxygen-based leaving group. The leaving group is trapped as its formic ester, and the aldehyde is reduced and subsequently esterified to a formate. Whereas the rearrangement to the aldehyde is catalyzed by sulfonic acids, the reduction step requires a unique catalyst system comprising a PdII or Pd0 precursor in loadings as low as 0.75 mol % and α,α′-bis(di-tert-butylphosphino)-o-xylene as ligand. The reduction step makes use of formic acid as an easy-to-handle transfer reductant. The substrate scope of the transformation encompasses both aromatic and aliphatic substrates and a variety of leaving groups.

Direct Synthesis of α-Alkoxy Ketones by Oxidative C–O Bond Formation

A convenient method to prepare α-alkoxy ketones has been developed by oxidative coupling of aryl methyl ketones and alcohols. With aqueous tert-butyl hydroperoxide (6.0 equiv.) as the oxidant, tetrabutylammonium iodide (20 mol-%) as the catalyst, and TsNHNH2(1.0 equiv.) as the additive, ketones underwent direct alkoxylation to give α-methoxy or α-ethoxy ketones in moderate to good yields.

Highly efficient synthesis of functionalized α-oxyketones: Via Weinreb amides homologation with α-oxygenated organolithiums

An efficient, chemoselective homologation of Weinreb amides to the corresponding variously substituted α-oxyketones has been developed via the addition of lithiated α-oxygenated species. This one-step, experimentally easy, high yielding protocol is amenable not only for accessing simple α-oxyketones but also for more complex substituted ones ranging from primary and secondary alkyl-type to aromatic ones. Full delivery of the stereochemical information contained in the starting materials is observed through both the employment of enantioenriched Weinreb amides and optically active organolithium species.

Flexible stereoselective functionalizations of ketones through umpolung with hypervalent iodine reagents

The functionalization of carbonyl compounds in the α-position has gathered much attention as a synthetic route because of the wide biological importance of such products. Through polarity reversal, or "umpolung", we show here that typical nucleophiles, such as oxygen, nitrogen, and even carbon nucleophiles, can be used for addition reactions after tethering them to enol ethers. Our findings allow novel retrosynthetic planning and rapid assembly of structures previously accessible only by multistep sequences. A Nu approach: An efficient α-functionalization of ketones with a range of simple and useful nucleophiles is possible by using hypervalent iodine reagents (see scheme; Nu′ can be the Nu itself or a protected form of this nucleophile group).

Experimental study on the reaction pathway of α-haloacetophenones with NaOMe: Examination of bifurcation mechanism

The reaction of PhCOCH2Br and NaOMe in MeOH gave PhCOCH 2OH as the major product and PhCOCH2OMe as the minor product. Substituent effects on the reactivity and product selectivity revealed that an electron-withdrawing substituent on the phenyl ring enhanced the overall reactivity and gave more alcohol than ether. It was indicated that the alcohol was formed via carbonyl addition-epoxidation, whereas the ether was formed by direct substitution. Substituent effects on the reaction rates, as well as the effects of NaOMe concentration on the rate and product ratio for both reactions of PhCOCH2Br and PhCOCH2CI are in line with the mechanism that the alcohol and ether products were formed via two independent and concurrent routes, carbonyl addition and a-carbon attack, respectively, and thus the reaction mechanism could be different from the bifurcation mechanism previously predicted for the reaction of PhCOCH2Br by a simulation study in the gas phase.

Oxidative iodination of carbonyl compounds using ammonium iodide and oxone

A simple, efficient, mild, and regioselective method for oxyiodination of carbonyl compounds has been reported by using NH4I as the source of iodine and Oxone as an oxidant. Various carbonyl compounds such as aralkyl ketones, aliphatic ketones (acyclic and cyclic), and β-keto esters proceeded to the respective α-monoiodinated products in moderate to excellent yields. Unsymmetrical aliphatic ketones reacted smoothly yielding a mixture of 1-iodo and 3-iodo ketones with the predominant formation of 1-iodoproduct.

Direct conversion of aromatic ketones to arenecarboxylic esters via carbon-carbon bond-cleavage reactions

Aromatic methyl ketones, ss-keto esters, and trifluoromethyl-l,3- diketones can be directly converted to arene-carboxylic esters via carbon-carbon bond cleavage of pyridinium iodide intermediates in the presence of copper(II) oxide, iodine, pyridine, and potassium carbonate in alcoholic media. The advantages of the present method in terms of good yields, mild reaction conditions, and inexpensive reagents should make this protocol a valuable alternative to the existing methods.

Decarbonylative diarylation of α-methoxyacetic acid yielding diarylmethanes mediated by Lewis acid and trifluoroacetic anhydride

Reaction of α-methoxyacetic acid with aromatic compounds in the presence of trifluoroacetic anhydride and Lewis acid has been found to give diarylmethanes. Some of the intermediates in this transformation have been identified via direct observation by 1H and 13CNMR spectroscopy. The reaction route has been clarified as follows: a mixed acid anhydride is formed from α-methoxyacetic acid and trifluoroacetic anhydride, which gives a hemiacylal type intermediate via decarbonylation followed by successive double electrophilic aromatic substitutions yielding diarylmethanes. Copyright