Oxidants Dess-Martin

The title compound is produced by treatment of 2-iodylbenzoic acid with acetic anhydride in acetic acid, and has found wide application as a mild oxidant ( Dess-Martin periodinane ) for ly and 2y alcohols. Although it appears not to be sensitive to impact, unlike the precursor acid, both explode violently when heated under confinement. The oxidant, on treatment with water is hydrolysed back to the explosive 2-iodylbenzoic acid. Forethought and caution are advised before using these explosive materials on any scale of working. 

There are problems associated with the expensive disposal of toxic waste from metal-based oxidations of alcohols. Thus, the focus has been largely on catalytic reactions as typified by Ley and Griffith s tetrapropylammonium perruthenate oxidant (section 7.1.6). Completely metal-free oxidations have much potential for environment-friendly oxidations, particularly if the reagent can be recovered and recycled. The most common metal-free oxidation of alcohols are TEMPO/oxone or TEMPO/N-chlorosuccinimide oxidation, Dess-Martin periodane oxidation (section 7.1.5) and Swern oxidation (section 7.1.4) and its several variants. 

Corey-Kim oxidation, Dess-Martin oxidation. Ley oxidation, Oppenauer oxidation, PTitzner-Moffatt oxidation. 

Using an oxidation/reduction sequence the g/wco-papulacandin 5.11 was also produced from 5.8. The dihydroxylation product of 5.8 was selectively protected at C-3 and the C-2 axial alcohol was oxidized (Dess-Martin) and reduced (DibalH) to intall the g/wco-stereochemistry, which upon TBS-deprotection give the gluco-isomer 5.11. 

This reaction is related to the Swern Oxidation, Dess Martin Oxidation, and Mojfatt-Swern Oxidation. 

Yeh M, Leitinger N, de Martin R, Onai N, Matsushima K, Vora DK, Berliner JA, Reddy ST. Increased transcription of IL-8 in endothelial cells is differentially regulated by TNF-alpha and oxidized phospholipids. Arterioscler Thromb Vase Biol 2001 21 1585-1591. 

Sanchez-Moreno C, Cano MP, De Ancos B, Plaza L, Olmedilla B, Granado F and Martin A. 2004b. Consumption of high-pressurized vegetable soup increases plasma vitamin C and decreases oxidative stress and inflammatory biomarkers in healthy humans. J Nutr 134(11) 3021—3025. 

The catalytic effects and versatility of cerinm(IV) ammonium nitrate as a single-electron oxidant were recently reviewed (Nair and Deepthi 2007, Maulide et al. 2007). However, it should be kept in mind that this oxidative reagent is very powerful and some sensitive fnnctions are not compatible with it. Particularly, some amines are at least as easily oxidizable as the starting molecule bearing the protected group. Anodic oxidation was proposed as a usefnl alternative (De Lamo Martin et al. 2005). 

LaplancheA, Orta de Velasquez M T, Boisdon V, Martin N, Martin G (1993) Modelisation of Micropollutant Removal in Drinking water Treatment by Ozonation or Advanced Oxidation Processes (03/H202), Ozone in Water and Wastewater Treatment-Proceedings of the 11th Ozone World Congress San Francisco, 17-90. 

Martin Jekel, Professor of Water Quality Control at the Technical University Berlin, has been involved in ozonation and oxidation research since 1976, especially concerning ozone/ biological activated carbon, microflocculation mechanisms of ozone and advanced oxidation processes for water and wastewaters. He studied chemistry, has a Ph.D. in chemical engineering and is a full professor since 1988. He contributed Chapter A 3 to this book. Technische Universitat Berlin, Institut fur Technischen Umweltschutz, Sekr. KF 4, Strasse des 17. Juni 135, D-10623 Berlin, Germany wrh itu201. ut.TU-Berlin.DE... 

Popular oxidation reactions of peptide alcohols such as the Parikh-Doering or Dess-Martin in addition to older oxidation reactions such as Collins, pyridinium chlorochromate, or Swern oxidation afford racemization free productsJ9121415 37-39 Oxidations using pyridinium dichromate results in racemization and low yields of product.[l3 Oxidation reactions have also been utilized in semisynthetic pathways of peptide aldehydes (1) peptide aldehydes are obtained through the enzymatic acylation of a peptide ester to an amino alcohol with subsequent oxidation of the peptide alcohol to afford the aldehyde, and (2) peptide aldehydes can also be obtained by direct enzymatic oxidation of the peptide alcohol by alcohol de-hydrogenaseJ40 41 ... 

Ti02, Ti02 on silicalite, and Ti-exchanged ZSM-5 show no electrochemical activity under the same conditions, suggesting that the nature and coordination state of the electroactive sites are characteristic of Tiiv in TS-1. A carbon electrode modified with TEOT undergoes reduction and oxidation processes at 0.62 and 0.71 V versus SCE, values only 60 mV different from those of TS-1. This indicates a close similarity between Tiiv in TEOT and Tiiv in TS-1 in both compounds the Ti,v ions are tetrahedrally coordinated by O and isolated from other TiIV ions (de Castro-Martins el al., 1993 ). 

Martin AR, Villegas I, La Casa C, de la Lastra CA. 2004. Resveratrol, a polyphenol found in grapes, suppresses oxidative damage and stimulates apoptosis during early colonic inflammation in rats. Biochem Pharmacol 67 1399-1410. 

Oxidation of 3-hydroxymethyl-2,3-dihydro-5H-pyrido[l,2,3-cfe][1,4] benzoxazin-5-ones with o-iodoxybenzoic acid in DMSO and with Dess-Martin periodinate in CH2CI2 afforded 3-formyl derivatives (08WOP2008/ 120003). Dehydrogenation of ethyl 10-[2-(ferf-butoxycarbonyl)-l,2,3,4,6,8a-hexahydropyrrolo[l,2-a]pyrazin-7-yl]-9-fluoro-3(S)-methyl-7-oxo-2,3-dihydro-7H-pyrido[l,2,3-de][l,4]oxazine-6-carboxylates in the presence of Pd/C with air in MeOH afforded 10-[2-(ferf-butoxycarbonyl)-l, 2,3,4-tetrahydropyrrolo[l,2-a]pyrazin-7-yl] derivatives, which then were deprotected (09BML4933). 

A4. Aguirre, F., Martin, I., Grinspon, D., Ruiz, M., Hager, A., de Paoli, T., Ihlo, J., Farach, H. A., and Poole, C. P. J., Oxidative damage, plasma antioxidant capacity, and glucemic control in elderly NIDDM patients. Free Radio. Biol. Med. 24, 580-585 (1998). 

Rotte C, Henze K, Muller M, Martin W (2000) Origins of hydrogenosomes and mitochondria -commentary. Curr Opin Microbiol 3 481-486 Saraste M (1999) Oxidative phosphorylation at the fin de siecle. Science 283 1488-1493 Sickmann A, Reinders J, Wagner Y, Joppich C, Zahedi R, Meyer HE, Schonfisch B, Perschil I, Chacinska A, Guiard B, Rehling P, Pfanner N, Meisinger C (2003) The proteome of Saccharomyces cerevisiae mitochondria. Proc Natl Acad Sci USA 100 13207-13212 Smith TF, Waterman MS (1981) Identification of common molecular subsequences. J Mol Biol 147 195-197... 

The first step of the total synthesis of 31 is the (7v )-proli nc-calal yzcd aldol reaction between 4 and 32, which gave the aldol adduct 33 with a good yield (69%) and nearly perfect stereocontrol (>96% de, >99% ee, Scheme 10). The same results were observed when the reaction was carried out on a 40-mmol scale yielding 5.22 g of 33 without a decrease of selectivity. The free hydroxyl group of 33 was quantitatively protected as MOM-ether. After hydrogenolytic debenzylation the aldehyde-ketone was obtained after Dess-Martin oxidation followed by a double Wittig reaction to provide the bisolefine 34 in 41% yield over 4 steps (Scheme 10). 

TMTt deprotection was performed in extremely careful conditions (1 min stirring at rt, five cycles, extensive washing) to avoid the cleavage of the DES linker oxidation with Dess-Martin reagent was performed successfully to give 3.123 (Fig. 3.44). 

Distlerath, L. M., Reilly, E E, B., Martin, M. V Wilkinson, G. R., and Guengerich, E E (1985). Immunochemical Characterization of the Human Liver Cytochrome P450 Involved in Debrisoquine Hydroxylation, In Microsomes and Drug Oxidations (A. R. Boobis, J. Caldwell, E De Matters, and C. R, Elcombe, eds.), Taylor Francis, London, pp. 380-389. 

De Munari, S., Frigerio, M., Santagostino, M. Hypervalent Iodine Oxidants Structure and Kinetics of the Reactive Intermediates in the Oxidation of Alcohols and 1,2-Diols by o-lodoxybenzoic Acid and Dess-Martin Periodinane. A Comparative 1H-NMR Study. J. Org. Chem. 1996, 61, 9272-9279. 

M. Thielmann, H. Dorge, C. Martin, S. Belosjorow, U. Schwanke, A. van De Sand, I. Konietzka, A. Buchcrt, A. Kruger, R. Schulz and Heusch G, Myocardial dysfunction with coronary microembolization signal transduction through a sequence of nitric oxide, tumor necrosis factor-alpha, and sphingosine, Circ. Res. 90(7), 807-813 (2002). 

Albee AL, Chodos AA (1970) Semiquantitative electron microprobe determination of Fe2+/Fe3+ and Mn2+/Mn3+ in oxides and silicates and its application to petrologic problems. Am Mineral 55 491-501 Alcacio , Hesterberg D, Chou JW, Martin JD, Beauchemin S, Sayers DE (2001) Molecular scale characteristics of Cu(II) bonding in goethite-humate complexes. Geochim Cosmochim Acta 65 1355-1366... 

Zb -112 Zb -237 Zb -325 flame retardant, polyamides Ethylenebis dibromonorbornane dicaiboximide, Octabromodiphenyl oxide flame retardant, polybutylenes Great Lakes DE-83 Great Lakes DE-83R Great Lakes SP-75 flame retardant, polyester fabric topcoats Solucote Top FR 767 flame retardant, polyester laminates Martinal ON-921... 

Hontoria-Lucas, C., Lopez-Peinado, A. J., DE D. Lopez-Gonzalez, J., Rojas-Cervantes, M. L., Martin-Aranda, R. M., (1995). Study of oxygen-containing groups in a series of graphite oxides physical and chemical characterization, Carbon, Vol. 33, No. 11, pp. 1585-1592 ISSN, 0008-6223. 

Seabra AB, Martins D, Simoes M, da Silva R, Brocchi M, de Oliveira MG. Antibacterial nitric oxide-releasing polyester for the coating of blood-contacting artificial materials. Artif Organs 2010 34 E204—14. http //dx.doi.Org/10.llll/j.1525-1594.2010. 00998.x. 

Mueller DN, De Souza RA, Yoo H, Martin M (2012) Phase stability and oxygen nonstoichiometry of highly oxygen-deficient Perovskite-type oxides a case study of (Ba,Sr)(Co,Fe)03 8. Chem Mater 24 (2) 269-274... 

Zaragoza-Martin F, Sopena-Escario D, MoraUon EC, Sahnas-Martinez de Lecea C. Pt/carbon nanofibers electrocatalysts for fuel cells Effect of the support oxidizing treatment. J Power Sources 2007 171 302-9. 

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