27739-28-2

Usage

InChI:InChI=1/C12H16O3/c1-9(2)8-15-12(13)10-4-6-11(14-3)7-5-10/h4-7,9H,8H2,1-3H3

Upstream product

• 615-37-2 ortho-methylphenyl iodide 
• 110-19-0 2-methylpropyl acetate 
• 3424-93-9 4-methoxyphenylacetamide 
• 78-83-1 2-methyl-propan-1-ol 
• 696-62-8 para-iodoanisole 
• 542-56-3 nitrous acid isobutyl ester 
• 121-97-1 4-Methoxypropiophenone 
• 34301-32-1 2-methyl-2-propenyl-4-methoxybenzoate 
• 100-07-2 4-methoxy-benzoyl chloride 
• 87117-15-5 1-methoxy-2,6-dimethylpyridinium methyl sulfate 
• 201230-82-2 carbon monoxide 
• 459-64-3 4-methoxybenzenediazonium tetrafluoroborate 
• 104-93-8 p-methylanizole 
• 105-13-5 4-Methoxybenzyl alcohol 

Relevant academic research and scientific papers

Mechanistic insight into the synergistic Cu/Pd-catalyzed carbonylation of aryl iodides using alcohols and dioxygen as the carbonyl source

Pd-catalyzed carbonylation, as an efficient synthetic approach to the installation of carbonyl groups in organic compounds, has been one of the most important research fields in the past decade. Although elegant reactions that allow highly selective carbonylations have been developed, straightforward routes with improved reaction activity and broader substrate scope remain long-term challenges for new practical applications. Here, we show a new type of synergistic Cu/Pd-catalyzed carbonylation reaction using alcohols and dioxgen as the carbonyl sources. A broad range of aryl iodides and alcohols are compatible with this protocol. The reaction is concise and practical due to the ready availability of the starting materials and the scalability of the reaction. In addition, the reaction affords lactones and lactams in an intermolecular fashion. Moreover, DFT calculations have been performed to study the detailed mechanisms. [Figure not available: see fulltext.]

Enolate-Based Regioselective Anti-Beckmann C-C Bond Cleavage of Ketones

The Baeyer-Villiger or Beckmann rearrangements are established methods for the cleavage of ketone derivatives under acidic conditions, proceeding for unsymmetrical precursors selectively at the more substituted site. However, the fragmentation regioselectivity cannot be switched and fragmentation at the less-substituted terminus is so far not possible. We report here that the reaction of ketone enolates with commercial alkyl nitrites provides a direct and regioselective way of fragmenting ketones into esters and oximes or ω-hydroxyimino esters, respectively. A comprehensive study of the scope of this reaction with respect to ketone classes and alkyl nitrites is presented. Control over the site of cleavage is gained through regioselective enolate formation by various bases. Oxidation of kinetic enolates of unsymmetrical ketones leads to the otherwise unavailable "anti-Beckmann"cleavage at the less-substituted side chain, while cleavage of thermodynamic enolates of the same ketones represents an alternative to the Baeyer-Villiger oxidation or the Beckmann rearrangement under basic conditions. The method is suited for the transformation of natural products and enables access to orthogonally reactive dicarbonyl compounds.

Electro-Oxidative Selective Esterification of Methylarenes and Benzaldehydes

A mild and green electro-oxidative protocol to construct aromatic esters from methylarenes and alcohols is herein reported. Importantly, the reaction is free of metals, chemical oxidants, bases, acids, and operates at room temperature. Moreover, the design of the electrolyte was found critical for the oxidation state and structure of the coupling products, a rarely documented effect. This electro-oxidative coupling process also displays exceptional tolerance of many fragile easily oxidized functional groups such as hydroxy, aldehyde, olefin, alkyne, as well as neighboring benzylic positions. The enantiomeric enrichment of some chiral alcohols is moreover preserved during this electro-oxidative coupling reaction, making it overall a promising synthetic tool.

Cobalt bis(acetylacetonate)–tert-butyl hydroperoxide–triethyl-silane: A general reagent combination for the Markovnikov-selective hydrofunctionalization of alkenes by hydrogen atom transfer

We show that cobalt bis(acetylacetonate) [Co(acac)2], tert-butyl hydroperoxide (TBHP), and triethylsilane (Et3SiH) constitute an inexpensive, general, and practical reagent combination to initiate a broad range of Markovnikov-selective alkene hydrofunctionalization reactions. These transformations are believed to proceed by cobalt-mediated hydrogen atom transfer (HAT) to the alkene substrate, followed by interception of the resulting alkyl radical intermediate with a SOMOphile. In addition, we report the first reductive couplings of unactivated alkenes and aryldiazonium salts by an HAT pathway. The simplicity and generality of the Co(acac)2–TBHP–Et3SiH reagent combination suggests it as a useful starting point to develop HAT reactions in complex settings.

Green alternative solvents for the copper-catalysed arylation of phenols and amides

Investigation of the use of green organic solvents for the Cu-catalysed arylation of phenols and amides is reported. Alkyl acetates proved to be efficient solvents in the catalytic processes, and therefore excellent alternatives to the typical non-green solvents used for Cu-catalysed arylation reactions. Solvents such as isosorbide dimethyl ether (DMI) and diethyl carbonate also appear to be viable possibilities for the arylation of phenols. Finally, a novel copper catalysed acyl transfer process is reported.

Intermolecular Hydropyridylation of Unactivated Alkenes

A general method for the hydropyridylation of unactivated alkenes is described. The transformation connects metal-mediated hydrogen atom transfer to alkenes and Minisci addition reactions. The reaction proceeds under mild conditions with high site-selectivities and allows for the construction of tertiary and quaternary centers from simple alkene starting materials.

Chemoselective dehydrogenative esterification of aldehydes and alcohols with a dimeric rhodium(II) catalyst

Dehydrogenative cross-coupling of aldehydes with alcohols as well as dehydrogentive cross-coupling of primary alcohols to produce esters have been developed using a Rh-terpyridine catalyst. The catalyst demonstrates broad substrate scope and good functional group tolerance, affording esters highly selectively. The high chemoselectivity of the catalyst stems from its preference for dehydrogenation of benzylic alcohols over aliphatic ones. Preliminary mechanistic studies suggest that the active catalyst is a dimeric Rh(ii) species, operating via a mechanism involving metal-base-metal cooperativity.

Palladium-catalysed oxidative cross-esterification between two alcohols

A simple palladium-catalysed oxidative cross-coupling between two different alcohols was developed. Various benzylic alcohols could couple with aliphatic alcohols in excellent yields. The use of benzyl chloride as the oxidant and the amount of aliphatic alcohol were both important for achieving the reaction selectivity.

Metal-free, room-temperature, radical alkoxycarbonylation of aryldiazonium salts through visible-light photoredox catalysis

The first radical alkoxycarboxylation of aryldiazonium salts using CO gas through visible-light-induced photoredox catalysis (16 W blue LEDs) has been developed. This reaction is entirely metal-free, is carried out at room temperature with a low loading of an organic dye as a photocatalyst (0.5 mol%), and provides a wide range of arylcarboxylic acid esters in high yields. Importantly, this photocatalytic system can be successfully extended to other carboxylation reactions.