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Effect of phosphorylation on the reaction rate of unnatural electrophiles with 2-keto-3-deoxy-6-phosphogluconate aldolase

Publication ,  Journal Article
Cotterill, IC; Shelton, MC; Machemer, DEW; Henderson, DP; Toone, EJ
Published in: Journal of the Chemical Society - Perkin Transactions 1
April 7, 1998

D-Glyceraldehyde is accepted as an electrophile by 2-keto-3-deoxy-6-phosphogluconate (KDPG) aldolase (EC 4.1.2.14) at 1% the rate of natural substrate, D-glyceraldehyde 3-phosphate. Accordingly, it was expected that addition of a phosphate moiety at C3 or C4 of unnatural aldehydes would enhance their activity as electrophilic substrates. Furthermore, phosphate would act as a useful protecting group during synthetic manipulations of the aldol adduct. A variety of phosphorylated and non-phosphorylated aldehydes were synthesized and evaluated as substrates for KDPG aldolase. Although small variations in reaction rate were observed, phosphorylation failed to provide a universal rate enhancement. Evaluation of substrate kinetic parameters revealed that the high rate of reaction of D-glyceraldehyde 3-phosphate compared to related electrophiles is entirely due to the efficiency of turnover with little change in binding exhibited among various substrates.

Duke Scholars

Published In

Journal of the Chemical Society - Perkin Transactions 1

DOI

ISSN

0300-922X

Publication Date

April 7, 1998

Issue

7

Start / End Page

1335 / 1341
 

Citation

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Cotterill, I. C., Shelton, M. C., Machemer, D. E. W., Henderson, D. P., & Toone, E. J. (1998). Effect of phosphorylation on the reaction rate of unnatural electrophiles with 2-keto-3-deoxy-6-phosphogluconate aldolase. Journal of the Chemical Society - Perkin Transactions 1, (7), 1335–1341. https://doi.org/10.1039/a706764j
Cotterill, I. C., M. C. Shelton, D. E. W. Machemer, D. P. Henderson, and E. J. Toone. “Effect of phosphorylation on the reaction rate of unnatural electrophiles with 2-keto-3-deoxy-6-phosphogluconate aldolase.” Journal of the Chemical Society - Perkin Transactions 1, no. 7 (April 7, 1998): 1335–41. https://doi.org/10.1039/a706764j.
Cotterill IC, Shelton MC, Machemer DEW, Henderson DP, Toone EJ. Effect of phosphorylation on the reaction rate of unnatural electrophiles with 2-keto-3-deoxy-6-phosphogluconate aldolase. Journal of the Chemical Society - Perkin Transactions 1. 1998 Apr 7;(7):1335–41.
Cotterill, I. C., et al. “Effect of phosphorylation on the reaction rate of unnatural electrophiles with 2-keto-3-deoxy-6-phosphogluconate aldolase.” Journal of the Chemical Society - Perkin Transactions 1, no. 7, Apr. 1998, pp. 1335–41. Scopus, doi:10.1039/a706764j.
Cotterill IC, Shelton MC, Machemer DEW, Henderson DP, Toone EJ. Effect of phosphorylation on the reaction rate of unnatural electrophiles with 2-keto-3-deoxy-6-phosphogluconate aldolase. Journal of the Chemical Society - Perkin Transactions 1. 1998 Apr 7;(7):1335–1341.

Published In

Journal of the Chemical Society - Perkin Transactions 1

DOI

ISSN

0300-922X

Publication Date

April 7, 1998

Issue

7

Start / End Page

1335 / 1341