Asymmetric induction by amino acid ligands in chromium(II)-assisted reduction of ketones

Gyarmati, J; Hajdu, Csongor; Dinya, Zoltán; Micskei, Károly; Zucchi, Claudia; Pályi, Gyula

doi:10.1016/s0022-328x(99)00227-2

Cited by 29 publications

(11 citation statements)

References 24 publications

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“…Over the past four decades, protein-based ArMs have been widely investigated to achieve a variety of valuable enantioselective transformations [1][2][3][4][5][6] . To precisely characterise the active centres and obtain insight into the reaction mechanisms of ArMs, simple scaffolds of peptides and amino acids have been employed to rationally design artificial metallo-peptides [7][8][9][10][11][12][13] and metalloamino acids [14][15][16][17][18][19][20][21] . In recent years, nucleic acids have aroused much interest among chemists for constructing diverse nucleic acid-based ArMs for enantioselective catalysis.…”

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confidence: 99%

A Cu(II)–ATP complex efficiently catalyses enantioselective Diels–Alder reactions

Wang

et al. 2020

Nat Commun

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Natural biomolecules have been used extensively as chiral scaffolds that bind/surround metal complexes to achieve stereoselectivity in catalytic reactions. ATP is ubiquitously found in nature as an energy-storing molecule and can complex diverse metal cations. However, in biotic reactions ATP-metal complexes are thought to function mostly as co-substrates undergoing phosphoanhydride bond cleavage reactions rather than participating in catalytic mechanisms. Here, we report that a specific Cu(II)-ATP complex (Cu2+·ATP) efficiently catalyses Diels-Alder reactions with high reactivity and enantioselectivity. We investigate the substrates and stereoselectivity of the reaction, characterise the catalyst by a range of physicochemical experiments and propose the reaction mechanism based on density functional theory (DFT) calculations. It is found that three key residues (N7, β-phosphate and γ-phosphate) in ATP are important for the efficient catalytic activity and stereocontrol via complexation of the Cu(II) ion. In addition to the potential technological uses, these findings could have general implications for the chemical selection of complex mixtures in prebiotic scenarios.

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confidence: 99%

A Cu(II)–ATP complex efficiently catalyses enantioselective Diels–Alder reactions

Wang

et al. 2020

Nat Commun

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“…10 Amplification of one molecule enantiomeric excess in consecutive one-pot Soai reaction cycles to macroscopically significant ees As the starting point the experience of the Debrecen group with the use of Cr(II) complexes in reduction of organic functional groups [127][128][129] was utilized, with the modification, that for N,O-donor ligands we chose pure enantiomers of amino acids. This reducing system was first tested in the reduction of various ketonic substrates [130][131][132], then with ketoximes [133]. In both cases medium to high enantiomeric excesses were found in the products.…”

Section: Toward Designed Soai-type Systems?mentioning

confidence: 99%

Stochastic and empirical models of the absolute asymmetric synthesis by the Soai-autocatalysis

et al. 2015

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Absolute asymmetric synthesis (AAS) is the preparation of pure (or excess of one) enantiomer of a chiral compound from achiral precursor(s) by a chemical reaction, without enantiopure chiral additive and/or without applied asymmetric physical field. Only one well-characterized example of AAS is known today: the Soai-autocatalysis. In an attempt at clarification of the mechanism of this particular reaction we have undertaken empirical and stochastic analysis of several parallel AAS experiments. Our results show that the initial steps of the reaction might be controlled by simple normal distribution ("coin tossing") formalism. Advanced stages of the reaction, however, appear to be of a more complicated nature. Symmetric beta distribution formalism could not be brought into correspondence with the experimental observations. A bimodal beta distribution algorithm provided suitable agreement with the experimental data. The parameters of this bimodal beta function were determined by a Pólya-urn experiment (simulated by computer). Interestingly, parameters of the resulting bimodal beta function give a golden section ratio. These results show, that in this highly interesting autocatalysis two or even perhaps three catalytic cycles are cooperating. An attempt at constructing a "designed" Soai-type reaction system has also been made.

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“…Biocatalysts are crucial components of these reactions and have gained special interest for the production of enantiopure alcohols from prochiral ketones in a cheap and environmentally friendly way . These chiral secondary alcohols can be synthesized using chemical catalysts, although this strategy has major drawbacks such as the use of toxic metals, poor level of enantioselectivity and low conversion, formation of undesirable products, and their expensiveness . Also, the enantioselectivity of the product is related to the complexity of the ligands.…”

Section: Introductionmentioning

confidence: 99%

“…2,3 These chiral secondary alcohols can be synthesized using chemical catalysts, although this strategy has major drawbacks such as the use of toxic metals, poor level of enantioselectivity and low conversion, formation of undesirable products, and their expensiveness. [4][5][6] Also, the enantioselectivity of the product is related to the complexity of the ligands. Some transition metals need additional enantiomeric ligands to achieve high enantioselectivity, and the cost of transition metals limits the use of industrialization processes.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of enantiopure (S)‐6‐chlorochroman‐4‐ol using whole‐cell Lactobacillus paracasei biotransformation

Şahin

2020

Chirality

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Chromane, which has a fused cyclic structure, is a significant molecule that can be found in the structure of many important compounds. Lactobacillus paracasei BD101 was demonstrated as whole‐cell biocatalyst for the synthesis of (S)‐6‐chlorochroman‐4‐ol with immense enantioselectivity. The conditions of asymmetric reduction were optimized one factor by one factor using L paracasei BD101 to achieve enantiomerically pure product and complete conversion. Using these obtained optimization conditions, asymmetric reduction of 6‐chlorochroman‐4‐one was performed under environmentally friendly conditions; 6‐chlorochroman‐4‐one, having a fused cyclic structure as previously noted to be difficult to asymmetric reduction with biocatalysts, was enantiomerically reduced to (S)‐6‐chlorochroman‐4‐ol with an enantiomeric excess >99% on a high gram scale. This study is the first example in the literature for the enantiopure synthesis of (S)‐6‐chlorochroman‐4‐ol using a biocatalyst. Also notably, the optical purity of (S)‐6‐chlorochroman‐4‐ol obtained in this study through asymmetric bioreduction using whole‐cell biocatalyst is the highest value in the literature. In this study, (S)‐6‐chlorochroman‐4‐ol was produced on a gram scale by an easy, inexpensive, and environmentally friendly method, which has shown the production of valuable chiral precursors for drug synthesis and other industrial applications. This study provides a convenient method for the production of (S)‐6‐chlorochroman‐4‐ol, which can meet the industrial green production demand of this chiral secondary alcohol.

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Asymmetric induction by amino acid ligands in chromium(II)-assisted reduction of ketones

Cited by 29 publications

References 24 publications

A Cu(II)–ATP complex efficiently catalyses enantioselective Diels–Alder reactions

A Cu(II)–ATP complex efficiently catalyses enantioselective Diels–Alder reactions

Stochastic and empirical models of the absolute asymmetric synthesis by the Soai-autocatalysis

Synthesis of enantiopure (S)‐6‐chlorochroman‐4‐ol using whole‐cell Lactobacillus paracasei biotransformation

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