Sodium periodate mediated oxidative transformations in organic synthesis

The formation of oximes and hydrazones is employed in numerous scientific fields as a simple and versatile conjugation strategy. This imine-forming reaction is applied in fields as diverse as polymer chemistry, biomaterials and hydrogels, dynamic combinatorial chemistry, organic synthesis, and chemical biology. Here we outline chemical developments in this field, with special focus on the past ∼10 years of developments. Recent strategies for installing reactive carbonyl groups and α-nucleophiles into biomolecules are described. The basic chemical properties of reactants and products in this reaction are then reviewed, with an eye to understanding the reaction's mechanism and how reactant structure controls rates and equilibria in the process. Recent work that has uncovered structural features and new mechanisms for speeding the reaction, sometimes by orders of magnitude, is discussed. We describe recent studies that have identified especially fast reacting aldehyde/ketone substrates and structural effects that lead to rapid-reacting α-nucleophiles as well. Among the most effective new strategies has been the development of substituents near the reactive aldehyde group that either transfer protons at the transition state or trap the initially formed tetrahedral intermediates. In addition, the recent development of efficient nucleophilic catalysts for the reaction is outlined, improving greatly upon aniline, the classical catalyst for imine formation. A number of uses of such second- and third-generation catalysts in bioconjugation and in cellular applications are highlighted. While formation of hydrazone and oxime has been traditionally regarded as being limited by slow rates, developments in the past 5 years have resulted in completely overturning this limitation; indeed, the reaction is now one of the fastest and most versatile reactions available for conjugations of biomolecules and biomaterials.

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“…57 This strategy can be used for facile modification of the glycoproteins of the glycocalyx by oxidizing sialic acid residues. 58 …”

Section: Functionalization Of Biomolecules For Oxime/hydrazone Ligmentioning

confidence: 99%

Oximes and Hydrazones in Bioconjugation: Mechanism and Catalysis

2017

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“…The alkali metals alts are obtained by neutralizing the solution with an appropriate base. Periodates are used extensively for variouso xidationr eactions in organic synthesis [44].A ss uch, both KIO 4 and NaIO 4 are availablec ommercially.A ni nformal survey of the catalog prices of major U. S. chemical retailers revealedt hat KIO 4 and NaIO 4 are approximately 2-3 times as expensive as the corresponding perchlorates.…”

Section: Issues and Concerns Regardingperiodate Oxidizersmentioning

confidence: 99%

Periodates as Potential Replacements for Perchlorates in Pyrotechnic Compositions

Brusnahan

Shaw

Moretti

et al. 2016

Propellants Explo Pyrotec

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The periodate salts NaIO4 and KIO4 are critically evaluated as potential replacements for KClO4 in pyrotechnic compositions. Key differences between the physical and chemical properties of the periodate and perchlorate oxidizers are presented. The thermochemical characteristics of binary flash/incendiary compositions containing Al, MgAl, or Mg as the fuel and periodate or perchlorate salts as oxidizers were studied using the FactSage 6.4 software package. The computational results are compared to existing experimental data. The tendency of NaIO4 to form gaseous Na, an emitter of yellow light, in such reactions promotes high luminous efficiencies. Due to a lack of literature addressing the stability and aging characteristics of periodate‐containing formulations, it is recommended that further research should be undertaken to evaluate potential chemical incompatibilities. Other concerns, including the availability and toxicological properties of the periodates, are also discussed.

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“…Since the earliest discovery in 1928 [26,27], the cleavage of 1,2-diols has been traditionally performed with stoichiometric high-valent inorganic oxidants, like periodates [28,29] or lead tetracarboxylates [30,31]. Occasionally, other reagents such as chromium trioxide [32,33], manganese dioxide [34,35], iron(III) trisphenantrolines [36], calcium hypochlorite [37], pyridinium chlorochromate [38], N-iodosuccinimide, [39] have been also used.…”

Section: 2-diolsmentioning

confidence: 99%