General Metal-Free Baeyer–Villiger-Type Synthesis of Vinyl Acetates

Abstract

Oxone, a cheap, stable, and nonhazardous oxidizing reagent, transforms α,β-unsaturated ketones of defined stereochemistry into their corresponding vinyl acetates through a Baeyer-Villiger reaction. This process is general and straightforward, tolerating a wide range of functional groups.

Direct oxidative esterification of toluene with 1,3‐dicarbonyl compounds catalysed by copper complex supported on magnetic nanoparticles

“…Traditionally, esters are often prepared by the nucleophilic addition of an alcohol to activated carboxylic acid derivatives such as acid anhydrides or chlorides . Further efforts have been devoted to the direct synthesis of esters using http://en.wikipedia.org/wiki/Steglich_esterification, http://en.wikipedia.org/wiki/Mitsunobu_reaction and Baeyer–Villiger oxidation . However, because of several reaction steps, production of unwanted by‐products, poor atom economy and difficulty of product isolation in all of the above three methods, it is one of the challenges of green and sustainable chemistry to update these old processes.…”

Oxidative esterification of methylarenes and 1,3‐dicarbonyls catalysed by copper chloride immobilized on magnetic nanoparticles

“…The disadvantages of those methods were poor atom economy, generation of troublesome wastes and use of hazardous reagents. These challenging problems led lots of interested scientists to propose some innovative strategies to make the synthesis of the ester bond greener, including the use of non‐toxic reagents like N , N ′‐dicyclohexylcarbodiimide (Steglich esterification), diazomethane and trialkyl or aryl phosphate‐diazo (Mitsunobu reaction), and other methods like Baeyer–Villiger oxidation …”

“…These challenging problems led lots of interested scientists to propose some innovative strategies to make the synthesis of the ester bond greener, including the use of nontoxic reagents like N,N′-dicyclohexylcarbodiimide (Steglich esterification), [5] diazomethane [5] and trialkyl or aryl phosphate-diazo (Mitsunobu reaction), [6,7] and other methods like Baeyer-Villiger oxidation. [8][9][10][11][12][13] However, because of poor atom economy and difficulty of product isolation in those procedures, metal-catalysed methods like oxidative carbonylation esterification of alcohols, [14][15][16] alkenes and alkynes [17][18][19][20][21][22] and arenes [23] have been developed in recent years.…”

Efficient Baeyer-Villiger electro-oxidation of ketones with molecular oxygen using an activated carbon fiber electrode in ionic liquid [bmim][OTf]

“…Traditional methods for performing such a transformation generally involve the use of stoichiometric amount of the strongest oxidizing reagents (e.g., trifluoroperacetic acid, peroxyacetic acid, and perbenzoic acid) [5][6][7][8], and suffer from considerable drawbacks such as low yield, harsh or delicate reaction condition, and a large amount of waste by-products. Various reagents employed as the oxygen donors have been developed for this conversion include sodium perborate [9], potassium peroxydisulfate (K 2 S 2 O 8 ) [10,11], sodium perborate (NaBO 3 ) [11], m-CPBA [12,13], NADPH [14,15], phenylacetone monooxygenase (PAMO) [16], H 2 O 2 [17][18][19][20][21][22], oxone [23], h-SiO 2 ·KHSO 5 [24], and other complexes [25][26][27][28][29][30]. However, some of these procedures are invariably associated with one or more disadvantages such as the use of expensive reagents, long reaction time, difficulties in work up, environmental hazards, and difficulties in recycling of the catalyst.…”