Oxidative methyl esterification of aldehydes promoted by molecular and hypervalent (III) iodine

Karade, Nandkishor N.; Budhewar, Vishnu H.; Katkar, A.N.; Tiwari, Girdharilal B.

doi:10.3998/ark.5550190.0007.b16

Cited by 39 publications

(12 citation statements)

References 10 publications

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“…Oxidation of aldehydes or primary alcohols by treatment with PhI(OAc) 2 ·I 2 in a methanol solution gives methyl esters 147 in high yields (Scheme ). , The experimental procedure for the oxidation of alcohols using 3-nitro-(diacetoxyiodo)benzene 148 and boron trifluoride ether complex as additive has been reported by Ochiai and co-workers . This BF 3 -catalyzed oxidation reaction probably involves a rapid ligand exchange on the iodine center with alcohols 149 to generate the alkoxyiodane intermediate 150 , followed by a rate-limiting reductive elimination of 3-nitroiodobenzene to produce carbonyl compounds 151 (Scheme ).…”

Section: Synthetic Applications Of Trivalent Iodine Compoundsmentioning

confidence: 99%

Advances in Synthetic Applications of Hypervalent Iodine Compounds

2016

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The preparation, structure, and chemistry of hypervalent iodine compounds are reviewed with emphasis on their synthetic application. Compounds of iodine possess reactivity similar to that of transition metals, but have the advantage of environmental sustainability and efficient utilization of natural resources. These compounds are widely used in organic synthesis as selective oxidants and environmentally friendly reagents. Synthetic uses of hypervalent iodine reagents in halogenation reactions, various oxidations, rearrangements, aminations, C−C bond-forming reactions, and transition metal-catalyzed reactions are summarized and discussed. Recent discovery of hypervalent catalytic systems and recyclable reagents, and the development of new enantioselective reactions using chiral hypervalent iodine compounds represent a particularly important achievement in the field of hypervalent iodine chemistry. One of the goals of this Review is to attract the attention of the scientific community as to the benefits of using hypervalent iodine compounds as an environmentally sustainable alternative to heavy metals.

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Section: Synthetic Applications Of Trivalent Iodine Compoundsmentioning

confidence: 99%

Advances in Synthetic Applications of Hypervalent Iodine Compounds

2016

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“…Although in the case of HVIC/R F –I mixtures, as seen above, the potential formation of CX 3 COOI (eq 3) can be neglected, rt reactions of I 2 with HVICs − ,,,, including IDAB, − ,− ,− IFAB, ,,− (ArOCH 2 COO) 2 IPh, CH 3 COOOH, − Hg(OAc) 2 , AgOAc, − AgOPr, CF 3 COOAg, ,− (CF 3 COO) 2 Hg, etc., , as well as with R alk –I, , do proceed with the quantitative and fast formation of CX 3 COOI, even in the dark.…”

Section: Controlled Radical Polymerization Of Vdfmentioning

confidence: 99%

“…CX 3 COOI species are quite reactive reagents: CH 3 COOI was employed in electrophilic aromatic iodinations, − ,,,,,, iodoacetoxylations of double ,,,− , and triple bonds, and alcohol oxidations. ,, Similarly, CF 3 COOI adds to alkenes and is a stronger electrophilic iodination reagent, ,− ,, which, by contrast to CH 3 COOI, , may iodinate even the parent PhI. , Moreover, CX 3 COOI from (CX 3 COO) 2 PhI/R alk –I ,, or CH 3 COOOH/R alk –I , may oxidize R alk I to the corresponding CX 3 COOR alk . , …”

Section: Controlled Radical Polymerization Of Vdfmentioning

confidence: 99%

Photomediated Controlled Radical Polymerization and Block Copolymerization of Vinylidene Fluoride

2016

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This review summarizes recent research on novel photochemical methods for the initiation and control of the polymerization of main chain fluorinated monomers as exemplified by vinylidene fluoride (VDF) and for the synthesis of their block copolymers. Such reactions can be carried out at ambient temperature in glass tubes using visible light. Novel, original protocols include the use of hypervalent iodide carboxylates alone or in conjunction with molecular iodine, as well as the use of photoactive transition metal carbonyls in the presence of alkyl, fluoroalkyl, and perfluoroalkyl halides. An in-depth study of the reaction parameters highlights the use of dimethyl carbonate as a preferred polymerization solvent and outlines the structure-property relationship for hypervalent iodide carboxylates and halide initiators in both the free radical and iodine degenerative transfer controlled radical polymerization (IDT-CRP) of VDF. Finally, the rational selection of metal carbonyls that are successful not only as IDT mediators but, more importantly, in the quantitative activation of both PVDF-CH2-CF2-I and PVDF-CF2-CH2-I chain ends toward the synthesis of well-defined PVDF block copolymers is presented.

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“…Over the past few decades, many organic and inorganic oxidants have been reported to have accomplished this process in alkaline alcoholic solutions. [13][14][15][16][17][18] Though this transformation has been widely studied, most of the achievements only cover methyl esters due to selectivity factors. In order to overcome this problem, new catalytic systems are highly desirable for this approach.…”

Section: Transition-metal-free Oxidation Of Aldehydes To Estersmentioning

confidence: 99%

Direct oxidative esterification of alcohols

et al. 2014

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Esterification is a fundamental transformation in chemistry. Traditional esterification only largely occurs between carboxylic acid derivatives and alcohols, and often involves multistep processes. Developments in the transition-metal-catalysed and metal-free direct esterification of alcohols under oxidative conditions has opened a door to the efficient, sustainable and environmentally friendly synthesis of esters from readily available materials. This Perspective gives an overview which covers the recent development of this emerging field.

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Oxidative methyl esterification of aldehydes promoted by molecular and hypervalent (III) iodine

Cited by 39 publications

References 10 publications

Advances in Synthetic Applications of Hypervalent Iodine Compounds

Advances in Synthetic Applications of Hypervalent Iodine Compounds

Photomediated Controlled Radical Polymerization and Block Copolymerization of Vinylidene Fluoride

Direct oxidative esterification of alcohols

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