Pyridinium phosphates

Dyer et al. oxidized a furanoside derivative by the DMSO-DCC-pyridinium phosphate method, and Albright and Goldman applied the Pfitzner-Moffatt procedure successfully for oxidation of yohimbine and other indole alkaloids. Suscep-... 

Mixed phosphoric acid diesters via pyridinium phosphate betaines... 

The use of chiral Bronsted acids as catalysts for enantioselective hetero-Diels-Alder reactions has also been examined by Akiyama [132, 133]. A BINOL-derived phosphoric acid [19,128, 134] was found to promote enantioselective cycloadditions of Brassard s diene 265 [135] to imines (Equation 27). Use of the corresponding pyridinium phosphate 266 resulted in higher yields along with high enantioselectivity for a range of imines, as exemplified by the formation of 267 (97% ee, 90% yield) [132]. 

The unknown phosphate ester had the same electrophoretic mobility as 2-deoxy ribitol 5-phosphate and it seemed reasonable to expect that in the conditions used (0.1 M pyridinium acetate buffer of pH 5) 2-deoxy ribitol-4- and -5-phosphates would behave similarly therefore it was considered probable that the unknown phosphate ester is 2-deoxy ribitol 4-phosphate, resulting from the reduction of the periodate resistant 2-deoxy ribose 4-phosphate. However, the possibility that both 2-deoxy ribitol 4-phosphate and 2-deoxy erythritol 3-phosphate (formed from... 

Explain what happens to (a) the pH of a solution of phosphoric acid after the addition of solid sodium dihydrogen phosphate (b) the percentage deprotonation of HCN in a hydrocyanic acid solution after the addition of hydrobromic acid (c) the concentration of H ions when pyridinium chloride is added to an aqueous solution of the base pyridine. 

Two types of amphiphilic quaternary 3-pyridinium ketoximes (253a, b) with different positioning of the hydrophobic alkyl chain have been synthesized and tested as hydrolytic micellar catalysts. A considerable positive deviation from the expected first-order curve was observed in the absorbance vs time plot when p-nitrophenyl diphenyl phosphate (252 R = Ph) and p-nitrophenyl diethyl phosphate... 

The same group expanded the scope of the aza-Diels-Alder reaction of electron-rich dienes to Brassard s diene 97 (Scheme 37) [60]. In contrast to Danishefsky s diene, it is more reactive, but less stable. Akiyama et al. found chiral BINOL phosphate (R)-3m (3 mol%, R = 9-anthryl) with 9-anthryl substituents to promote the [4 + 2] cycloaddition of A-arylated aldimines 94 and Brassard s diene 97. Subsequent treatment with benzoic acid led to the formation of piperidinones 98. Interestingly, the use of its pyridinium salt (3 mol%) resulted in a higher yield (87% instead of 72%) along with a comparable enantioselectivity (94% ee instead of 92% ee). This method furnished cycloadducts 98 derived from aromatic, heteroaromatic, a,P-unsaturated, and aliphatic precursors 94 in satisfactory yields (63-91%) and excellent enantioselectivities (92-99% ee). NMR studies revealed that Brassard s diene 97 is labile in the presence of phosphoric acid 3m (88% decomposition after 1 h), but comparatively stable in the presence of its pyridinium salt (25% decomposition after 1 h). This observation can be explained by the fact that the pyridinium salt is a weak Brpnsted acid compared to BINOL phosphate 3m. 

Some commonly used buffers, such as sodium and potassium phosphate, are incompatible with ELSD, but there are ready alternatives. For example, ammonium acetate has similar buffering properties to potassium phosphate, and ammonium carbonate, ammonium formate, pyridinium acetate, and pyridinium formate are options for different pH ranges. Typical mobile phase modifiers that do not meet the volatility criteria can be replaced by a wide variety of more volatile alternates. For example, phosphoric acid, commonly used as an acid modifier fo control pH and ionization, can be replaced by trifluoroacetic acid other acids that are sufficiently volatile for use with FLSD include, acetic, carbonic, and formic acids. Triethylamine, commonly used as a base modifier, is compatible with FLSD other base modifiers that can be used are ethylamine, methylamine, and ammonium hydroxide [78]. 

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