You are using Science Of Synthesis as a Guest.
Please login to access the full content or check if you have access via1.3.3.4.2.2 Phosphorylation of Carbohydrates by Pyrophosphate
Please login to access the full content or check if you have access via
Wever, R.; Babich, L.; Hartog, A. F., Science of Synthesis: Biocatalysis in Organic Synthesis, (2015) 1, 235.
Acid phosphatases catalyze the regioselective phosphorylation of the ribose group in inosine.[16,70] Later it was shown that many simple carbohydrates can also be phosphorylated using acid phosphatases from Shigella flexneri (PhoN-Sf) and Salmonella enterica (PhoN-Se)[70,77–79] using pyrophosphate as the phosphate donor. In particular, d-glucose is phosphorylated in a very efficient manner, as has also been observed using the enzyme from Raoultella planticola.[80] The efficient conversion of glucose into d-glucose 6-phosphate (4) has been used in a three-enzyme cascade system containing glucose 6-phosphate dehydrogenase (EC 1.1.1.49) to regenerate nicotinamide adenine dinucleotide phosphate (NADPH), which was used to produce chiral alcohols from ketones.[78] d-Glucose 6-phosphate (4) has also been synthesized in a preparative manner by this enzymatic method (Scheme 10).[79] The yield is 76% based upon pyrophosphate; however, on the basis of the input of glucose, the yield is considerably less and amounts to only 7.6%. Much better conversions (19%) are obtained in fed-batch reactions with acid phosphatase from Shigella flexneri (PhoN-Sf) immobilized on Immobeads.[77] Interestingly, unlike other primary phosphorylated carbohydrates, d-glucose 6-phosphate (4) once formed is hardly dephosphorylated by PhoN-Sf and the incubation time is not very critical. The productivity of the synthesis of d-glucose 6-phosphate using a continuous-flow reactor has also been tested and high yields were obtained.[77] Using this reactor, 2-acetamido-2-deoxy-d-glucose can also be phosphorylated, providing product 7 (R1 = NHAc) in 53% yield (Scheme 11).[77] Considering the ease of preparation, these continuous-flow reactors with immobilized acid phosphatase have significant advantages compared to classical synthetic chemistry methods. The success of this continuous-flow system is mainly due to very high stability of the immobilized acid phosphatase. During turnover the system is stable for at least 2 weeks and the column can be repetitively used for the preparation of other phosphorylated carbohydrates and alcohols.
Meeeee 88 Meeeeeeeeeeeeee ee Meeeeee[88]
Meeeee 88 Meeeeeeeeeeeeee ee Meeeeee eee 8-Meeeeeeee-8-eeeee-e-eeeeeee Meeee e Meeeeeeeee-Meee Meeeeee[88]
M8 | Meeee (%) | Mee |
---|---|---|
MM | 88 | [88] |
MMMe | 88 | [88] |
Meeeeeeeeeee Meeeeeeee
e-Meeeeee 8-Meeeeeeee (8); Meeeeee Meeeeeeee:[88]
M eeeeeee (8 eM) eeeeeeeeee 888 eM eeeeeeeeeeeee eee 8 M e-eeeeeee ee 888 eM eeeeeee eeeeee (eM 8.8) eee eeeeeee ee 88 °M. Mee eeeeeeee eee eeeeeee ee eee eeeeeeee ee 8 µM eeee eeeeeeeeeee eeee Meeeeeee eeeeeeee (MeeM-Me). Meeeeeeeee eeeeeee 88.8% eeeee ee eeeeeeeeeeeee eeeee 88 e. Mee eM eee eeeeeeee ee 8.8 eeee MeMM, eee eeeeeeeee eee eeeeeeeeeeee ee eee eeeeeeee ee 8.8 M Me(MMe)8 (8 eM). Mee eeeeeeeeeee eee eeeeee eeee M8M (8 × 8 eM). Meee MeMM (eeeee eeeeeeeeeeeee 88%) eee eeeee ee eee eeeeeeee ee eeeeeeeeeee eee eeeeee eeee ee e-eeeeeee 8-eeeeeeeee, eeeee eee eeeeee eeee 88% MeMM (8 eM) eeeee eeeeeeeeee. Meeeee (MMM) eeeeeeee ee e eeeee eeeee (8.888 e; >88% eeee, eeeeeeeeee ee MMMM). Mee eeeeeeeeeee eee eeeeeeeee eeeee eee-eeeeeeee eeeee (Meeee 88M8) ee M+ eeee. Meee eeeeeeeee eeeeeeee ee 88.8% eeeeeeee ee eee eeeeee e-eeeeeee 8-eeeeeeeee (8); eeeee: 88.8% (eeeee ee eeeeeeeeeeeee).
e-Meeeeee 8-Meeeeeeee (8, M8 = MM); Meeeeee Meeeeeeee Meeee e Meee Meeeeee:[88]
M eeee eee eeeeeeee eeeeeeeeee 888 eM eeeeeee eee 888 eM Me8M8M8M8. Mee eM eee 8. Meee eee eeeeee ee e eeee eeee ee 8.88 eM · eee−8 eeeeeee e 8.8-eM eeeeee eeeeeeeeee eeee eeeeeeeeeee eeee Meeeeeee eeeeeeee (MeeM-Me) eeeeeeeeeee ee Meeeeeeee. Meeee 88 e, e eeee (888 eM) eee eeeeeeeee eeee eeeeeeeee 888 eM e-eeeeeee 8-eeeeeeeee. Meee eee eeeeeee ee ee eeee 8% (e/e) Me(MMe)8 ee eM 8 ee eeeeee eeee eeeeeeeee. Meeee 8 e, eee eeeeeee eee eeeeeeee; eee eeeee eeee ee eeeeee eeeeeeeee eee eeeeeeeee, eeeeeee eee eeeeeeee eeeeeeeeee e-eeeeeee, eeeeeeeeeeeeee eeeeeee, eee eeeeeee eee eeeeeeeeeeee. Meee eee eeeeeeee ee eeeeeeeeeeeee ee e-eeeeeee 8-eeeeeeeee (8, M8 = MM) eeee 8 eeeeeee ee eeee MeMM ee eM 8 eee eeeeeee ee 8 °M. Meeee 8 e, eee eeeeeee eee eeeeeeee eee eee eeeeee eeee ee eeeeeeeeeeeeee eeeeeee eee eeeee eee eeeeeeeeeeeee; eeeee: 88 e. Meee eeeeeeeeeee ee e eeeeeeee ee 88% ee eee e-eeeeeee 8-eeeeeeeee eeee eee eeeeeee, eeeee ee eee eeeeeeeeeeeee.
8-Meeeeeeee-8-eeeee-e-eeeeeee 8-Meeeeeeee (8, M8 = MMMe); Meeeeee Meeeeeeee Meeee e Meee Meeeeee:[88]
M eeee eee eeeeeeee eeeeeeeeee 888 eM 8-eeeeeeeee-8-eeeee-e-eeeeeee eee 888 eM eeeeeeeeeeeee eeee e eM eee ee 8.8 ee eeeeee Me8M8M8M8 eee Me8M8M8. Meee eee eeeeee (8.88 eM · eee−8) eeeeeee e 8.8-eM eeeeee eeeeeeeeee eeee eeeeeeeeeee eeee Meeeeeee eeeeeeee (MeeM-Me) eeeeeeeeeee ee Meeeeeeee. Meeee 88 e, e eeee (888 eM) eeeeeeeeee 88–88 eM 8-eeeeeeeee-8-eeeee-e-eeeeeee 8-eeeeeeeee eee eeeeeeee eeee eeeee 8-eeeeeeeee-8-eeeee-e-eeeeeee 8-eeeeeeeee (8, M8 = MMMe) eee eeeeeeee ee e eeeeee eeee; eeeee: 88.8 e (88%, eeee eeeeeee ee 8-eeeeeeeee-8-eeeee-e-eeeeeee).
References
[16] | Meeeee, M.-e.; Meeeeeee, M.; Meeeee, M.; Meeeee, M.; Meeee, M., Meee. Meee. Mee. Mee., (8888) 88, 888. |
[70] | Meeeee, M.; Meeee, M.; Meeeee, M. M.; eee Meee, M.; Meeee, M., Mee. Meeeee. Meee., (8888) 8, 8888. |
[77] | Meeeee, M.; Meeeee, M. M.; eee eee Meeee, M. M.; Meeee, M., Meee.–Mee. M., (8888) 88, 8888. |
[78] | Meeeee, M. M.; eee Meee, M.; Meeee, M., Mee. Meeee. Meeee., (8888) 888, 8888. |
[79] | eee Meee, M.; Meeeee, M. M.; eee eee Meee, M. M.; Meeee, M., Mee. Meeee. Meeee., (8888) 888, 8888. |
[80] | Méeeee, M.; Meeeeeeeeeee, M. M.; Meeeee, M. M.; Meeeeee, M. M.; Meeeeeeee, M. M.; Meeeeeeee, M. M., Meee. Meeeeeeee. Meeeeeeeee., (8888) 88, 8888. |