Biocatalytic Reductions: From Lab Curiosity to “First Choice”

Wildeman, Stefaan M. A. De; Sonke, Theo; Schoemaker, Hans E.; May, Oliver

doi:10.1021/ar7001073

Cited by 229 publications

(119 citation statements)

References 66 publications

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“…[27][28][29] The hydroxyl group of the aldimine is vital for the high reactivity and enantioselectivity. 30,31 Moreover, studies show that the hydroxyl group could stabilize ␣ anions in the presence of base (Scheme 1). 32,33 Therefore, we initiated our studies with salicylic aldimine (4a) and p-methyl arylsulfonyl imine (5a) in the presence of different catalysts in toluene at room temperature (Fig.…”

Section: Resultsmentioning

confidence: 99%

First example of an organocatalytic asymmetric Mannich reaction between aldimines of glycinates and sulphonyl imines

et al. 2016

Can. J. Chem.

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Abstract:The catalytic enantioselective Mannich-type reaction between glycinate Schiff base and imines has been one of the most efficient routes for accessing ␣,␤-diamino acids. However, the glycinate Schiff bases used in the references were almost ketimines. Only several examples of aldimines were used in the presence of metal catalyst. We developed the first example of an asymmetric direct Mannich reaction using aldimines of glycinates instead of ketimines of glycinates. The reaction was well catalyzed by chiral guanidine with high yield (up to 92%) and moderate stereoselectivity (up to 65%).Key words: organocatalyst, aldimine, glycinates, sulphonyl imine, chiral guanidine.Résumé : La réaction catalytique énantiosélective de type Mannich entre des glycinates, utilisés comme base de Schiff, et des imines se révèle être l'une des voies les plus efficaces pour accéder à des acides ␣,␤-diaminés. Cependant, dans les articles de référence, les glycinates utilisés comme base de Schiff sont presque toujours des cétimines. Il n'existe que peu d'exemples où des aldimines ont été utilisées en présence d'un catalyseur métallique. Nous avons mis au point le premier exemple d'une réaction de Mannich asymétrique directe où des aldimines de glycinates sont utilisés à la place de cétimines de glycinates. La catalyse de cette réaction, dont le rendement était élevé (jusqu'à 92 %), était convenablement assurée par une guanidine chirale, et ce, avec une stéréosélectivité modérée (jusqu'à 65 %). [Traduit par la Rédaction]

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Section: Resultsmentioning

confidence: 99%

First example of an organocatalytic asymmetric Mannich reaction between aldimines of glycinates and sulphonyl imines

et al. 2016

Can. J. Chem.

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“…[1,2,30] Reductive amination is an important natural biosynthetic reaction [12,13] that, via natural protein enzymes, has found utility in laboratory synthesis [14] and in industry. [15] The present work suggests that reductive amination by nucleic acid catalysts should be more broadly examined, perhaps in RNA World contexts by ribozymes. Others have commented upon the potential importance of reductive amination in such contexts, [16,17] especially given the importance of nucleotide-based cofactors such as NAD(P)H in extant biochemistry.…”

mentioning

confidence: 86%

“…[13] In vitro, enzymatic reductive amination is important in both laboratory-scale [14] and industrial-scale organic synthesis. [15] Reductive amination may also have been important in RNA World scenarios. [16,17] Our unexpected discovery of DNA-catalyzed reductive amination suggests further exploration of the abilities of nucleic acid enzymes to catalyze this interesting and potentially useful class of reaction.…”

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confidence: 99%

DNA‐Catalyzed Reductive Amination

Wong¹,

Mulcrone²,

Silverman³

2011

Angewandte Chemie

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Keywordsdeoxyribozymes; DNA; in vitro selection; reductive amination Deoxyribozymes are particular DNA sequences that have catalytic ability, analogous to protein enzymes as functional amino acid sequences. [1,2] The discovery of natural RNA enzymes (ribozymes) spurred the search for artificial deoxyribozymes, [3] which are identified by in vitro selection. [4] Most deoxyribozyme-catalyzed reactions involve phosphodiester bond cleavage or ligation, [5][6][7] although other reactions such as Diels-Alder reaction [8] and thymine dimer photoreversion [9] have also been reported.We have initiated a comprehensive effort to identify deoxyribozymes that catalyze reactions of amino acid side chains, initially focusing on small peptide substrates and with the longerterm goal of covalently modifying large proteins. [10] Towards this goal, as part of a recent study we examined the ability of several new deoxyribozymes to modify tyrosine (or serine) side chains of tripeptide substrates that are not covalently tethered to the deoxyribozyme, although the tether was required to enable the selection process. [11] Deoxyribozymes identified using tethered peptide substrates were also active with untethered peptide substrates, but with substantially lower rate and yield. Therefore, in new experiments, here we performed in vitro selection directly using untethered peptide substrates. This effort required a modified selection procedure that was intended to involve reductive amination as a step merely to "capture" catalytically active DNA sequences. Surprisingly, this selection process provided deoxyribozymes that operate entirely independently of the tripeptide substrate and instead catalyze a Ni 2+ -dependent reductive amination involving the N 2 -amine of a guanosine nucleobase on an RNA substrate, which reacts with an oligonucleotidedialdehyde substrate. Reductive amination is a key biochemical process, e.g. for amino acid biosynthesis and catabolism using amino acid dehydrogenases (oxidases) [12] and transaminases (aminotransferases). [13] In vitro, enzymatic reductive amination is important in both laboratory-scale [14] and industrial-scale organic synthesis. [15] Reductive amination may also have been important in RNA World scenarios. [16,17] Our unexpected discovery of DNA-catalyzed reductive amination suggests further exploration of the abilities of nucleic acid enzymes to catalyze this interesting and potentially useful class of reaction.For any in vitro selection strategy that does not involve physical compartmentalization or segregation of individual candidate sequences, [18] the selection design must include a mechanism by which individual, functional sequences become separable from the vast excess of nonfunctional sequences. Importantly, this mechanism must operate in parallel fashion without requiring independent interrogation (i.e., screening) of each candidate [5] A key advantage of the gel-shift approach is that functional sequences are separated largely on the basis of oligonucleotide length (size), which has incr...

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“…The highest turn-over number (TTN) value for NAD recycling reported in the literature is >1,000,000 [86]. The pharmaceutical industry nearly stops further efforts in increasing TTN values of ~10,000-100,000 [87,88] due to high selling values of chiral compounds plus the additional regulatory requirements if the current process is modified. But it is vital that TTN values of NAD should be higher than 10 6 for the economically viable production of biocommodities [31].…”

Section: Sypab Challenges and Opportunitiesmentioning

confidence: 99%

Renewable Hydrogen Carrier — Carbohydrate: Constructing the Carbon-Neutral Carbohydrate Economy

Zhang

Mielenz

2011

Energies

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Abstract:The hydrogen economy presents an appealing energy future but its implementation must solve numerous problems ranging from low-cost sustainable production, high-density storage, costly infrastructure, to eliminating safety concern. The use of renewable carbohydrate as a high-density hydrogen carrier and energy source for hydrogen production is possible due to emerging cell-free synthetic biology technology-cell-free synthetic pathway biotransformation (SyPaB

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Biocatalytic Reductions: From Lab Curiosity to “First Choice”

Cited by 229 publications

References 66 publications

First example of an organocatalytic asymmetric Mannich reaction between aldimines of glycinates and sulphonyl imines

First example of an organocatalytic asymmetric Mannich reaction between aldimines of glycinates and sulphonyl imines

DNA‐Catalyzed Reductive Amination

Renewable Hydrogen Carrier — Carbohydrate: Constructing the Carbon-Neutral Carbohydrate Economy

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