Unexpected dehomologation of primary alcohols to one-carbon shorter carboxylic acids using o-iodoxybenzoic acid (IBX)

Xu, Shu; Itto, Kaori; Satoh, Motohiko; Arimoto, Hirokazu

doi:10.1039/c3cc49160a

Cited by 16 publications

(8 citation statements)

References 22 publications

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“…This novel reaction has been used for the oxidation of various alcohols 558 to one carbon shorter carboxylic acid 559 in good yields (Scheme 160). 1397 The authors of that paper isolated and investigated by 1 H and 13 C NMR the active species formed from IBX and molecular iodine under reaction conditions; however, the exact structure of this highly reactive intermediate remains unknown.…”

Section: Noncyclic and Pseudocyclic Iodylarenesmentioning

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: Noncyclic and Pseudocyclic Iodylarenesmentioning

confidence: 99%

Advances in Synthetic Applications of Hypervalent Iodine Compounds

2016

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“…Although there are cases of formate being generated from aromatic aldehyde in enzymatic Baeyer-Villiger oxidations that use cyclohexanone monooxygenase and 4-hydroxyacetophenone monooxygenase of microbial origin (26)(27)(28), an enzyme that generates formate from aliphatic aldehyde has yet to be discovered. In organic chemistry, an efficient transformation of a primary alcohol to a one-carbon-shorter carboxylic acid using o-iodoxybenzoic acid and iodine has recently been reported (29). In the present study, the predicted arthropod enzyme would catalyze a novel dehomologation and generate a one-carbonshorter primary alcohol from an aldehyde via hydrolysis of formate.…”

Section: Discussionmentioning

confidence: 87%

Biosynthetic pathway of aliphatic formates via a Baeyer–Villiger oxidation in mechanism present in astigmatid mites

Shimizu

Sakata

Schmelz

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

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Astigmatid mites depend on bioactive glandular secretions, pheromones, and defensive agents to mediate intra- and interspecies interactions. Aliphatic formates, such as (Z,Z)-8,11-heptadecadienyl formate (8,11-F17) and (Z)-8-heptadecenyl formate (8-F17), are rarely encountered natural products that are abundant inSancassaniasp. Sasagawa (Acari: Acaridae) mite secretions. Linoleic acid and oleic acid are predicted as key intermediates in the synthesis of the closely related aliphatic formates. To gain insight in this biosynthetic pathway, acarid mite feeding experiments were conducted using13C-labeled precursors to precisely track incorporation. Analyses using13C NMR spectroscopy demonstrated that the13C-labeling pattern of the precursors was detectable on formates in exocrine secretions and likewise on fatty acids in total lipid pools. Curiously, the results demonstrated that the formates were biosynthesized without the dehomologation of corresponding fatty acids. Careful examination of the mass spectra from labeling experiments revealed that the carbonyl carbon of the formates is originally derived from the C-1 position of the fatty acids. Consistent with a Baeyer–Villiger oxidation reaction, labeling studies support the insertion of an oxygen atom between the carbonyl group and carbon chain. Empirical data support the existence of a Baeyer–Villiger monooxygenase responsible for the catalyzation of the Baeyer–Villiger oxidation. The predicted existence of a Baeyer–Villiger monooxygenase capable of converting aliphatic aldehydes to formates represents an exciting opportunity to expand the enzymatic toolbox available for controlled biochemical synthesis.

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“…Although a few examples of oxidative dehomologation of alcohols using chromium‐based reagents or Cu–NHC–TEMPO (NHC: N‐heterocyclic carbene, TEMPO: 2,2,6,6‐tetramethylpiperidin‐1‐oxy) complexes have been reported, the reactions suffered from low product yields and poor selectivities. The recent discovery of o ‐iodoxybenzoic acid (IBX) by the group of Arimoto allowed for selective dehomologation of primary alcohols to afford carboxylic acids with one carbon atom less, thus indicating a considerable improvement of the oxidative dehomologation process . However, unreacted IBX and o ‐iodobenzoic acid hampered the isolation of the desired carboxylic acid from the reaction mixture and the protocol required an additional additive (I 2 ) and high temperature (Scheme b).…”

Section: Methodsmentioning

confidence: 99%

“…The recent discovery of o-iodoxybenzoic acid (IBX) by the group of Arimoto allowed for selectived ehomologation of primary alcohols to afford carboxylic acids with one carbon atom less, thus indicating ac onsiderable improvemento ft he oxidative dehomologation process. [6] However, unreactedI BX and o-iodobenzoic acid hampered the isolation of the desired carboxylic acid from the re-action mixture and the protocol required an additional additive (I 2 )a nd high temperature (Scheme 1b).…”

mentioning

confidence: 99%

“…In particular,b oth electron-withdrawingsubstituted and unsubstituted alcohols were fully converted to the corresponding benzoic acids with high purity (> 99 %), thus requiring no further purification ( Table 2, entries 1-3). On the other hand, alcohols with electron-donatings ubstituents underwent incomplete conversion, but extremely high selectivities were also observed in these cases ( Table 2, entries [6][7][8]. It is noteworthy that in all cases no aryl acetic acid derivatives (2) were obtained as directly oxidized products.…”

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confidence: 99%

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Metal‐Free Chemoselective Oxidative Dehomologation or Direct Oxidation of Alcohols: Implication for Biomass Conversion

et al. 2015

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A transition metal-free, chemoselective reaction was performed using the sodium tert-butoxide-oxygen (NaO(t) Bu-O2 ) system, resulting in either oxidative dehomologation or direct oxidation of alcohols. In particular, the newly developed protocol may be used to predict the major product formed, which depends on alkyl chain length of the alcohols and reaction conditions. The rational mechanism of this transformation was also demonstrated by performing an (18) O isotopic labelling experiment. This protocol presents a straightforward method for biomass conversion of a lignin model compound to phenol and benzoic acid.

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Unexpected dehomologation of primary alcohols to one-carbon shorter carboxylic acids using o-iodoxybenzoic acid (IBX)

Abstract: A novel and efficient transformation of primary alcohols to one-carbon shorter carboxylic acids using IBX is reported. Mechanistic studies revealed that the combination of IBX and molecular iodine produces a different active hypervalent iodine species.

Cited by 16 publications

References 22 publications

Advances in Synthetic Applications of Hypervalent Iodine Compounds

Advances in Synthetic Applications of Hypervalent Iodine Compounds

Biosynthetic pathway of aliphatic formates via a Baeyer–Villiger oxidation in mechanism present in astigmatid mites

Metal‐Free Chemoselective Oxidative Dehomologation or Direct Oxidation of Alcohols: Implication for Biomass Conversion

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