Aldolase-catalyzed synthesis

Yu, H. and Chen, X. (2006) Aldolase-catalyzed synthesis of beta-D-Gal-(l-9)-D-KDN a novel acceptor for sialyltransferases. Organic Letters, 8, 2393-2396. 

Scheme 11. Aldolase-catalyzed synthesis of statin drugs via the megagenonuc approach...

Scheme 5.24 Aldolase-catalyzed synthesis of different pancrastatin analogues.

Scheme 5.25 Aldolase-catalyzed synthesis of three stereoisomers of sialyl Lewis X mimetics.

Novel Strategies in Aldolase-catalyzed Synthesis of Iminosugars... 

Figure 19.8 D-fructose-6-bisphosphate aldolase-catalyzed synthesis of D-fagomine (11).

Figure 4. Sialic acid aldolase-catalyzed synthesis of fluorosialic acid and related substances, (a) Normal reaction, (b) synthesis of 9-fluoro-9-deoxy-N-acetylneuraminic acid, (c) synthesis of 7,9-difluoro-7,9-dideoxy-D-g/ycero-L-a-a/tro-2-nonulopyranosonic acid, (d) synthesis of S-fluoro-3,5-dideoxy-D-g/ycero-a-D-gu/o-2-nonuIopyranosonic acid...

Figure 23 Aldolase-catalyzed synthesis of oligosaccharides bearing sialic acid at the reducing end. In this example, pyruvate (in red) was condensed with Glc a1-6 Man to produce Glc a1-9 KDN.

Some observations indicate that the stereochemical outcome of the reaction seems to be under thermodynamic control, and stereochemistry at C-4 can be reversed. For example, in the Neu5Ac aldolase catalyzed synthesis of KDO, a mixture of (5)-C-4 and (7 )-C-4 were isolated when D-arabinose was the substrate (Scheme 5) [47,48]. 

R. Duncan, D.G. Drueckhammer, Preparation of deoxy sugars via aldolase-catalyzed synthesis of 1-deoxy-l-thioketoses, 1. Org. Chem. 61 (1996) 438-439. 

J. Calveras, M. Egido-Gabas, L. G6mez, I. Casas, T. Parella, I. loglar, I. Bujons, P. Clap, Dihydroxyacetone phosphate aldolase-catalyzed synthesis of structurally diverse polyhy-droxylated pyrrolidine derivatives and evaluation of their glycosidase inhibitory properties, Chem. Eur. J. 15 (2009) 7310-7328. 

HMG-CoA REDUCTASE INHIBITORS ALDOLASE-CATALYZED SYNTHESIS OF CHIRAL LACTOL... 

HMG-CoA reductase inhibitors aldolase-catalyzed synthesis of chiral lactol. 

The exploitation of FSA-like aldolases represents a qualitative progress in aldolase-catalyzed synthesis as these enzymes accept diverse donors with the hitherto unique requirement of the hydroxymethylcarbonyl moiety. A systematic study of potential donor substrates with iimovative functionalities and structures is still necessary to assess the potential of these catalysts. Additionally, further mutagenic works on the active site may provide FSA-like aldolases with broader structural tolerance for both donor and acceptor substrates, which would be of paramount utility in organic synthesis. A significant limitation of the FSA-like aldolases is the lack of a set of stereocomplementary enzymes, which has not been found in nature yet. 

Laborda, R, Sayago, F. J., Cativiela, C., Parella, T., Joglar, J., and Clapes, P., Aldolase-catalyzed synthesis of conformationally constrained iminocyclitols Preparation of polyhydroxylated benzopyrrolizidines and cyclohexapyrrolizidines. Org. Lett. 2014,... 

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