Rabbit muscle aldolase as a catalyst in organic synthesis

Bednarski,; Simon, Es; Bischofberger, Norbert; Fessner, W.-D.; Kim, Mj; Lees, Watson J.; Saito, Takeshi; Waldmann, Herbert; Whitesides, G. M.

doi:10.1021/ja00184a034

Cited by 221 publications

(86 citation statements)

References 8 publications

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“…Reaction with GA was not considered following pathway B. Indeed, GA was reported to be a good acceptor substrate for FBA that would lead to the formation of D-xylulose-1-phosphate [16] as by-product.…”

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confidence: 99%

One‐Pot Cascade Reactions using Fructose‐6‐phosphate Aldolase: Efficient Synthesis of D‐Arabinose 5‐Phosphate, D‐Fructose 6‐Phosphate and Analogues

et al. 2012

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Abstract. One-pot multienzymatic reactions have been performed for the synthesis of 1-deoxy-D-fructose-6-phosphate, 1,2-dideoxy-D-arabino-hept-3-ulose-7-phosphate, D-fructose-6-phosphate and D-arabinose-5-phosphate. The whole strategy is based on a fructose-6-phosphate aldolase (FSA) mediated aldol key step as a part of three or four enzymes-catalysed cascade reactions. The four known donors for FSA dihydroxyacetone (DHA), hydroxy acetone (HA), 1-hydroxy-2-butanone (HB) and glycolaldehyde (GA) were used with D-glyceraldehyde-3-phosphate as the acceptor substrate. The target phosphorylated sugars were obtained in good to excellent yields and high purity.

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confidence: 99%

One‐Pot Cascade Reactions using Fructose‐6‐phosphate Aldolase: Efficient Synthesis of D‐Arabinose 5‐Phosphate, D‐Fructose 6‐Phosphate and Analogues

et al. 2012

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“…In the condensation reaction it is specific for dihydroxyacetone phosphate with retention of pro-S-configuration of C-3 in the ketoses. More than 50 different aldehydes are condensed with DHAP (23,24).…”

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confidence: 99%

Carbon Isotope Effects on the Fructose-1,6-bisphosphate Aldolase Reaction, Origin for Non-statistical 13C Distributions in Carbohydrates

Gleixner

Schmidt

1997

Journal of Biological Chemistry

120

107

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The kinetic and equilibrium isotope effects on the fructose-1,6-bisphosphate aldolase reaction have been determined using the rabbit muscle enzyme. The natural 13 C abundance for both atoms participating in the bond splitting were measured in position C-1 of dihydroxyacetone phosphate and glyceraldehyde 3-P after irreversible conversion to glycerol-3-P and 3-phosphoglycerate, respectively, and chemical degradation. The carbon isotope effects were determined comparing the 13 C content of the corresponding positions after partial and complete turnover, and after complete equilibration of the reactants. 13 (V max /K m ) on C-3 was 1.016 ؎ 0.007 and 0.997 ؎ 0.009 on position C-4, and the equilibrium isotope effects K 12 /K 13 on these positions were 1.0036 ؎ 0.0002 and 1.0049 ؎ 0.0001.The observed kinetic isotope effect on C-3 is discussed to originate from the formation of the enamine, which comes to equilibrium before the rate determining release of glyceraldehyde 3-P from the ternary complex. The equilibrium isotope effect is seen as the reason for an earlier-found relative 13 C enrichment in position C-3 and C-4 of glucose and for varying enrichments in 13 C of carbohydrates from different compartments of cells. The kinetic isotope effect is suggested to cause 13 C discriminations in the C-3 pool in context with the hexose formation in competition with other dihydroxyacetone phosphate turnover reactions.The relative enrichment of carbon-13 in the carboxyl group of amino acids, as observed by Abelson and Hoering (1) in 1961, was the first indication for the existence of non-statistical isotope distributions in biological compounds. Later results on acetic acid (2) and on acetoin (3) gave evidence that this observation was just one example of a common phenomenon. In order to find a general explanation for this observation Galimov (4) discussed that even in chemically unequilibrated systems, e.g. biological systems, a microscopic reversibility in enzymatic reactions is the origin for a thermodynamically ordered isotope distribution. The author's calculations could in fact explain some of the isotopic patterns of natural compounds known at that time. However, the presumption of a general thermodynamic equilibrium in biological systems is probably not realistic. In our opinion kinetic isotope effects on enzymatic reactions should be considered as primary causes for isotope discriminations. This has been proven for the primary CO 2 -fixing reactions (5-8). In secondary metabolism, the isotope effect on the pyruvate dehydrogenase reaction has been made responsible for the general depletion of 13 C in metabolites of acetyl-CoA, such as fatty acids or isoprenoids (9 -15).More detailed interpretations were possible when the total isotopic patterns of primary and secondary metabolites became available. Especially, our corresponding investigations on glucose indicated an enrichment of 13 C in positions C-3 and C-4, and a depletion of 13 C in positions C-1 and C-6 (Fig. 1) of this important primary metabolite (16). We have a...

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“…Introduction not react (2). Furthermore, aromatic aldehydes are either poor substrates or are unreactive.…”

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1,3-Dioxan-5-ones: synthesis, deprotonation, and reactions of their lithium enolates

Majewski¹,

Gleave²,

Nowak³

1995

Can. J. Chem.

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A general synthetic route to 2-alkyl-and 2,2-dialkyl-1,3-dioxan-5-ones, using tris(hydroxymethy1)-nitromethane as the starting material, is described. Deprotonation of these compounds was studied. It was established that these dioxanones could be deprotonated with LDA; however, the reduction of the carbonyl group via a hydride transfer from LDA, giving the corresponding dioxanols, often competed with deprotonation. The reduction could be minimized by using Corey's internal quench procedure to form silyl en01 ethers and was less pronounced in 2,2-dialkyldioxanones (ketals) than in 2-alkyldioxanones (acetals). Self-aldol products were observed when dioxanone lithium enolates were quenched with H,O. Addition reactions of lithium enolates of dioxanones to aldehydes were threo-selective as predicted by the Zimmerman-Traxler model. Dioxanones having two different alkyl groups at the 2-position were deprotonated enantioselectively by chiral lithium amide bases with enantiomeric excess (ee) of up to 70%.

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Rabbit muscle aldolase as a catalyst in organic synthesis

Cited by 221 publications

References 8 publications

One‐Pot Cascade Reactions using Fructose‐6‐phosphate Aldolase: Efficient Synthesis of D‐Arabinose 5‐Phosphate, D‐Fructose 6‐Phosphate and Analogues

One‐Pot Cascade Reactions using Fructose‐6‐phosphate Aldolase: Efficient Synthesis of D‐Arabinose 5‐Phosphate, D‐Fructose 6‐Phosphate and Analogues

Carbon Isotope Effects on the Fructose-1,6-bisphosphate Aldolase Reaction, Origin for Non-statistical 13C Distributions in Carbohydrates

1,3-Dioxan-5-ones: synthesis, deprotonation, and reactions of their lithium enolates

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