Alcohols, amino, periodate oxidation

Geoghegan, K.E, and Stroh, J.G. (1992) Site-directed conjugation of nonpeptide groups to peptides and proteins via periodate oxidation of a 2-amino alcohol. Applications to modification at N-terminal serine. Bioconjugate Chem. 3, 138-146. 

The sensitivity to periodate of Ser and Thr is thousands of times greater than that of the better known periodate oxidation of 1,2-cis-diols, for example in the sugars of glycoproteins.19 This means that the concentration of reagent can be kept very low, in only small excess over the l-amino-2-alcohol, and the reaction time kept short (3 to 10 min). It is, thus, usually possible to avoid oxidative attack of the side chains of Met, Trp, and His, but some risk of... 

The Malaprade Periodic Acid Oxidation Reaction oxidizes 1,2 diols or 2-amino alcohols with periodic acid ... 

Deltaline is the acetyl ester of the amino alcohol deltamine (XLVIII, eldelidine) and treatment of the latter with acid produced demethylene-deltamine (XLIX) 19, 36). It was first believed that in the periodate oxidation of XLIII, 3 moles of NalOg was consumed and this led to the conclusion that XLIII contains four adjacent hydroxyls 19), an assumption later shown to be incorrect by the same authors 37). Apparently,... 

This mechanism is supported by the fact that every 3-oxoalkylarsonic acid studied also eliminated arsenite. First, 3-hyroxypropylarsonic acid proved to be a substrate for alcohol dehydrogenase from yeast, and similarly eliminated arsenite. Further, the oxidation by periodate of the HO—CH2—CHOH—CH2—CH2—As03H2, expected to produce 0=CH—CH2—CH2—As03H2 (another 3-oxoalkylarsonic acid), also yielded arsenite, and conditions that normally transaminate amino acids, when applied to the glutamate analogue HOOC—CH(—NH2)—... 

Pure homoallylic alcohols are converted into y-amino-p-hydroxy acids by protection as the TBDMS ether or A(0-acetonide followed by degradative oxidation of the terminal alkene using a catalytic amount of ruthenium(III) chloride and sodium periodate (Scheme... 

Novel nor-seco baccatin 99 was synthesized in 92% yield through oxidative cleavage of the A ring of 14-OH-DAB (75) with periodic acid via the hydroxy ketone intermediate 100 (Scheme 19). Protection of the 7-hydroxyl of 99 as TES ether followed by reduction of the aldehyde with sodium borohydride yielded nor-seco baccatin alcohol 101 in 80% yield. Nor-seco 13-amino-baccatins 102 and 103 were synthesized from 101 and 99a via the Mitsunobu reaction and reductive amination, respectively, in high yields (Scheme 20). 

The synthesis of isolongistrobine also started with the imidazole ester 126, which in three steps was converted to the amino alcohol 129. Acylation with 4-pentenoyl chloride gave the amide alcohol 133. Oxidation of 133 with chromium trioxide in aqueous pyridine yielded the 4-pentene carboxamide 134. Oxidative splitting of the vinyl group of 134 with sodium periodate... 

In addition to the oxidative scission of 1,2-diols, the reaction can be extended to related 1,2-bifunc-tional compounds such as oxiranes, 1,2-dicarbonyl compounds, 2-hydroxy aldehydes, ketones and acids, a-amino alcohols, 1,2-diamines and also to polyols. LTA cleaves a-hydroxy acids much more readily than do periodates and both reagents oxidize 2-hydroxy aldehydes and 1,2-dicarbonyl compounds relatively slowly. Only periodic acid in water reacts with oxiranes via the corresponding diols. 

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