Carbon selective isotopic labeling

Benzoates. The selective debenzoylation of sucrose octabenzoate [2425-84-5] using isopropylamine in the absence of solvents caused deacylation in the furanose ring to give 2,3,4,6,1/3/6 -hepta- and 2,3,4,6,1/6 -hexa-O-benzoyl-sucroses in 24.1 and 25.4% after 21 and 80 hours, respectively (54). The unambiguous assignment of partially benzoylated sucrose derivatives was accompHshed by specific isotopic labeling techniques (54). Identification of any benzoylated sucrose derivative can thus be achieved by comparison of its C-nmr carbonyl carbon resonances with those of the assigned octabenzoate derivative after benzoylation with 10 atom % benzoyl—carbonyl chloride in pyridine. 

A dual isotope labeling technique [85] has been used to measure membrane permeability in plant cells, based on the selective permeabiHty of the membranes of living cells to tritiated water and carbon-14 labeled mannitol. Kieran [29] showed that the results of the dual isotope labeling and Evan s Blue staining methods correlated well as indicators of cell viability however, the latter was preferable in terms of reagent cost and ease of analysis. 

Among the classic methods for the extension of the aldose chain by one carbon atom from the reducing end [9J, the Kiliani-Fischer cyanohydrin synthesis [10] is a milestone in carbohydrate chemistry. However after 110 years from discovery and numerous applications [11], including the preparation of carbon and hydrogen isotopically labeled compounds for mechanistic and structural studies [12], there are still several drawbacks that make the method impractical. These are the low and variable degree of selectivity and the harsh reaction conditions that are required to reveal the aldose from either the aldonic acid or directly from the cyanohydrin. Synthetic applications that have appeared in recent times confirmed these limitations. For instance, a quite low selectivity was registered [13] in the addition of the cyanide ion to the D-ga/acfo-hexodialdo-l,5-pyranose derivative 1... 

The method can be simultaneously applied to each atom of interest. An atom that is expected to have a negligible KIE is selected as an internal standard. For example, with the methyl group as the internal standard, the KIE for every other position in isoprene was determined for the Diels-Alder reaction with maleic anhydride. This method is especially useful for the measurement of carbon isotope effects, where normal methods require synthesis of isotopic labeled reactants. 

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