Even though enzymes are the cornerstones of living systems, it has so far proven difficult to deploy artificial catalysts in a biological setting. Organocatalysts are arguably well-suited artificial catalysts for this purpose because, compared with enzymes and inorganic catalysts, they are simpler, often less toxic and widely accessible. This Review describes how organocatalysts that operate in aqueous media might enable us to selectively access new chemical transformations and provide new possibilities for chemical biology and biomedicine. Organocatalysts can be categorized according to the mechanisms by which they activate substrates, drawing comparisons with enzymes. We describe the characteristics of a catalyst that are necessary for biological compatibility and in vivo applicability, and use these to evaluate a selection of organocatalytic reactions. The attributes of the catalyst (such as functional groups and pKa values) and the reaction (such as the microenvironment surrounding intermediates) are key considerations when developing efficient organocatalysis in aqueous media. Although we only know of a limited set of organocatalytic reactions with biological potential, on the basis of recent developments we expect a bright future for organocatalysis in biology, to the benefit of chemical biology and biomedicine.

/pdf/organocatalysis-in-aqueous-media-51qhhd61r5.pdf

Organocatalysis in aqueous media

Having been inspired by formose-based hypotheses surrounding the origin of life, we report on a novel catalytic route toward a series of recently discovered four-carbon α-hydroxy acids (AHA) and their esters from accessible and renewable glycolaldehyde (GA) in various solvents. The synthesis route follows a cascade type reaction network, and its mechanism with identification of the rate-determining step was investigated with in situ 13C NMR. The mechanistic understanding led to optimized reaction conditions with higher overall rates of AHA formation by balancing Bronsted and Lewis acid activity, both originating from the tin halide catalyst. An optimal H+/Sn ratio of 3 was identified, and this number was surprisingly irrespective of the Sn oxidation state. Further rate enhancement was accomplished by adding small amounts of water to the reaction mixture, boosting the rate by a factor of 4.5 compared with pure methanol solvent. The cascade reaction selectively yields near 60% methyl-4-methoxy-2-hydroxybuta...

Toward Functional Polyester Building Blocks from Renewable Glycolaldehyde with Sn Cascade Catalysis

The key role of carbohydrates in biological processes and their visible existence in our everyday life have stimulated the interest of leading research groups on the smart and simple synthesis of common and rare sugar molecules. Now, more than 120 years after Fischer's first synthesis of (D)-glucose (1890), we are witnessing important development in this field of total synthesis. Using modern methods of direct activation of carbonyl compounds chemists can prepare sugars in an elegant and efficient way similar to that of Nature. This tutorial review presents recent impressive progress in the area of de novo synthesis of carbohydrates by using organocatalytic direct aldol reaction as a key step.

Organocatalytic synthesis of carbohydrates

Asymmetric organocatalysis often operates under near ambient conditions, which means it is air and moisture compatible. However, in many examples water is indeed necessary for achieving excellent catalytic results. Ranging from the addition of small amounts of water to a reaction, to complex catalytic systems in the presence of water as the only reaction medium, this review offers an illustrative classification of the uses of water in asymmetric organocatalysis.

/pdf/water-in-asymmetric-organocatalytic-systems-a-global-1quzn0quwm.pdf

Water in asymmetric organocatalytic systems: a global perspective.

This paper reports an investigation into organocatalytic hydrogels as prebiotically relevant systems. Gels are interesting prebiotic reaction media, combining heterogeneous and homogeneous characte...

Catalytic Gels for a Prebiotically Relevant Asymmetric Aldol Reaction in Water: From Organocatalyst Design to Hydrogel Discovery and Back Again

Efficient asymmetric organocatalytic formation of erythrose and threose under aqueous conditions

Esters of proteinogenic amino acids efficiently catalyse the formation of erythrose and threose under potentially prebiotic conditions in the highest yields and enantioselectivities yet reported. Remarkably while esters of (L)-proline yield (L)-tetroses, esters of (L)-leucine, (L)-alanine and (L)-valine generate (D)-tetroses, offering the potential to account for the link between natural (L)-amino acids and natural (D)-sugars. The effect of pH and NaCl on the yields and enantioselectivities was also investigated and was shown to be significant, with the optimal enantioselectivities occurring at pH 7.

http://www.chtf.stuba.sk/~szolcsanyi/education/files/Chemia%20heterocyklickych%20zlucenin/Prednaska%207/Doplnkove%20studijne%20materialy/Formose%20reaction/Asymmetric%20organocatalytic%20formation%20of%20protected%20and%20unprotected%20tetroses%20under%20potentially%20prebiotic%20conditions.pdf

Asymmetric organocatalytic formation of protected and unprotected tetroses under potentially prebiotic conditions

Ethyl ester of N-methyl-L-leucine is applied as a chiral catalyst for the aldol dimerization of aldehyde (I).

Efficient Asymmetric Organocatalytic Formation of Erythrose and Threose under Aqueous Conditions.

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Efficient asymmetric organocatalytic formation of erythrose and threose under aqueous conditions

Asymmetric organocatalytic formation of protected and unprotected tetroses under potentially prebiotic conditions

Efficient Asymmetric Organocatalytic Formation of Erythrose and Threose under Aqueous Conditions.