Enantioselective Friedel–Crafts reactions in water catalyzed by a human telomeric G-quadruplex DNA metalloenzyme

Wang, Changhao; Li, Yinghao; Jia, Guifang; Liu, Yan; Lü, Shouqin; Li, Can

doi:10.1039/c2cc31320k

Cited by 116 publications

(73 citation statements)

References 44 publications

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“…4 In addition, the Li group 5 found that double-stranded DNA from herring sperm is capable of catalyzing the dithioacetalization in water for a variety of aldehydes under mild reaction conditions. Recently, G-quadruplex DNA has been demonstrated as a promising catalyst for enantioselective Diels–Alder 6–8 and Friedel–Crafts 9 reactions.…”

Section: Introductionmentioning

confidence: 99%

DNA-based asymmetric catalysis: role of ionic solvents and glymes

Zhao

Shen

2014

RSC Adv.

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Recently, DNA has been evaluated as a chiral scaffold for metal complexes to construct so called ‘DNA-based hybrid catalysts’, a robust and inexpensive alternative to enzymes. The unique chiral structure of DNA allows the hybrid catalysts to catalyze various asymmetric synthesis reactions. However, most current studies used aqueous buffers as solvents for these asymmetric reactions, where substrates/products are typically suspended in the solutions. The mass transfer limitation usually requires a long reaction time. To overcome this hurdle and to advance DNA-based asymmetric catalysis, we evaluated a series of ionic liquids (ILs), inorganic salts, deep eutectic solvents (DES), glymes, glycols, acetonitrile and methanol as co-solvents/additives for the DNA-based asymmetric Michael addition. In general, these additives induce indistinguishable changes to the DNA B-form duplex conformation as suggested by circular dichroism (CD) spectroscopy, but impose a significant influence on the catalytic efficiency of the DNA-based hybrid catalyst. Conventional organic solvents (e.g. acetonitrile and methanol) led to poor product yields and/or low enantioselectivities. Most ILs and inorganic salts cause the deactivation of the hybrid catalyst except 0.2 M [BMIM][CF3COO] (95.4% ee and 93% yield) and 0.2 M [BMIM]Cl (93.7% ee and 89% yield). Several other additives have also been found to improve the catalytic efficiency of the DNA-based hybrid catalyst (control reaction without additive gives >99% ee and 87% yield): 0.4 M glycerol (>99% ee and 96% yield at 5 °C or 96.2% ee and 83% yield at room temperature), 0.2 M choline chloride/glycerol (1:2) (92.4% ee and 90% yield at 5 °C or 94.0% ee and 88% yield at room temperature), and 0.5 M dipropylene glycol dimethyl ether (>99% ee and 87% yield at room temperature). The use of some co-solvents/additives allows the Michael addition to be performed at a higher temperature (e.g. room temperature vs 5 °C) and a shorter reaction time (24 h vs 3 days). In addition, we found that a brief pre-sonication (5 min) of DNA in MOPS buffer prior to the reaction could improve the performance of the DNA-based hybrid catalyst. We have also shown that this DNA-based catalysis method is suitable for a variety of different substrates and relatively large-scale reactions. In conclusion, a judicious selection of benign co-solvents/additives could improve the catalytic efficiency of DNA-based hybrid catalyst.

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Section: Introductionmentioning

confidence: 99%

DNA-based asymmetric catalysis: role of ionic solvents and glymes

Zhao

Shen

2014

RSC Adv.

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“…In contrast, under molecular crowding conditions, ODN-1-4 all displayed parallel conformations ( Figure S3 a-d). Although the reactions catalyzed by the DNA-Cu 2+ complex of ODN-1-4 all produce the opposite enantiomer of product 3 a, the enantioselectivities vary with different loop sequences (Table 4, entries [5][6][7][8]. These observations suggest that the loop sequence plays a crucial role in Table S4).…”

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“…[4] Very recently, a G4DNA metalloenzyme composed of G4DNA and copper(II) ions has been reported to be able to catalyze an enantioselective Friedel-Crafts reaction. [5] This biology/chemistry interface is an attractive area of research and awaits further extensive exploration. Herein, we report an enantioselective D-A reaction achieved through the use of human telomeric G4DNA-based catalysts.…”

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Enantioselective Diels–Alder Reactions with G‐Quadruplex DNA‐Based Catalysts

et al. 2012

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Deoxyribonucleic acid (DNA) is the genetic material of living organisms. In the past, double-stranded DNA (dsDNA) with its ubiquitous architecture has not been regarded as a catalytic species, since the duplex structure precludes the formation of catalytically competent tertiary structures. [1] To date, although no naturally occurring catalytic DNA has been reported, DNA for nonbiological applications has aroused much interest in chemists for applications in areas such as catalysis, encoding, and stereocontrol. [2] Among these applications, a series of DNA-based asymmetric catalysis have been developed, which use a hybrid catalyst composed of dsDNA and a copper(II) complex. [3] This same strategy was later applied to G-quadruplex DNA (G4DNA) and modest enantioselectivities in the Diels-Alder (D-A) reaction were obtained. [4] Very recently, a G4DNA metalloenzyme composed of G4DNA and copper(II) ions has been reported to be able to catalyze an enantioselective Friedel-Crafts reaction. [5] This biology/chemistry interface is an attractive area of research and awaits further extensive exploration. Herein, we report an enantioselective D-A reaction achieved through the use of human telomeric G4DNA-based catalysts. We show that the absolute configuration of the products can be reversed when the conformation of the G4DNA is switched from antiparallel to parallel. Furthermore, both the reaction rate and the enantioselectivity of the reaction were found to be dependent on the DNA sequence.The D-A reaction is an important carbon-carbon bond forming reaction in organic synthesis. In the past few decades, it has received much attention in the development of innovative catalytic strategies to control the creation of the new carbon-carbon bonds and stereocenters. Among those strategies, biological molecules have been viewed as interesting and promising catalysts. [6] Herein, human telomeric G4DNA (ODN-1, 5'-G 3 (T 2 AG 3 ) 3 -3') was selected owing to its tunable conformation. As an initial attempt, a model D-A reaction [7] between aza-chalcone (1 a) and cyclopentadiene (2) was chosen to probe the catalytic performance of ODN-1. We found that ODN-1 alone in its antiparallel conformation [8] could promote the D-A reaction and the enantiomeric excess of the endo isomer of product 3 a is 17 % (Table 1, entry 2).The enantioselectivity of the ODN-1 promoted D-A reaction is significantly higher than that of the uncatalyzed reaction (Table 1, entry 2 vs. entry 1), which suggests that ODN-1 might function as an enantioselective catalyst for the D-A reaction.We assembled a complex between Cu(NO 3 ) 2 and ODN-1 (ODN-1-Cu 2+ ) and tested its ability to enantioselectively catalyze the D-A reaction. ODN-1-Cu 2+ provides a significant enhancement in the reaction rate (Table 1, entry 4) compared with the rates observed with ODN-1 (Table 1, entry 2) or Cu(NO 3 ) 2 (Table 1, entry 3). We also observed an excellent diastereoselectivity for product 3 a (endo/exo of 98:2) and a good enantioselectivity (74 % ee). These results suggest that ODN-1...

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“…[5] This biology/chemistry interface is an attractive area of research and awaits further extensive exploration. Herein, we report an enantioselective D-A reaction achieved through the use of human telomeric G4DNA-based catalysts.…”

mentioning

confidence: 99%

Enantioselective Diels–Alder Reactions with G‐Quadruplex DNA‐Based Catalysts

et al. 2012

Self Cite

View full text Add to dashboard Cite

Deoxyribonucleic acid (DNA) is the genetic material of living organisms. In the past, double-stranded DNA (dsDNA) with its ubiquitous architecture has not been regarded as a catalytic species, since the duplex structure precludes the formation of catalytically competent tertiary structures.[1] To date, although no naturally occurring catalytic DNA has been reported, DNA for nonbiological applications has aroused much interest in chemists for applications in areas such as catalysis, encoding, and stereocontrol.[2] Among these applications, a series of DNA-based asymmetric catalysis have been developed, which use a hybrid catalyst composed of dsDNA and a copper(II) complex.[3] This same strategy was later applied to G-quadruplex DNA (G4DNA) and modest enantioselectivities in the Diels-Alder (D-A) reaction were obtained.[4] Very recently, a G4DNA metalloenzyme composed of G4DNA and copper(II) ions has been reported to be able to catalyze an enantioselective Friedel-Crafts reaction. [5] This biology/chemistry interface is an attractive area of research and awaits further extensive exploration. Herein, we report an enantioselective D-A reaction achieved through the use of human telomeric G4DNA-based catalysts. We show that the absolute configuration of the products can be reversed when the conformation of the G4DNA is switched from antiparallel to parallel. Furthermore, both the reaction rate and the enantioselectivity of the reaction were found to be dependent on the DNA sequence.The D-A reaction is an important carbon-carbon bond forming reaction in organic synthesis. In the past few decades, it has received much attention in the development of innovative catalytic strategies to control the creation of the new carbon-carbon bonds and stereocenters. Among those strategies, biological molecules have been viewed as interesting and promising catalysts.[6] Herein, human telomeric G4DNA (ODN-1, 5'-G 3 (T 2 AG 3 ) 3 -3') was selected owing to its tunable conformation. As an initial attempt, a model D-A reaction [7] between aza-chalcone (1 a) and cyclopentadiene (2) was chosen to probe the catalytic performance of ODN-1. We found that ODN-1 alone in its antiparallel conformation [8] could promote the D-A reaction and the enantiomeric excess of the endo isomer of product 3 a is 17 % (Table 1, entry 2).The enantioselectivity of the ODN-1 promoted D-A reaction is significantly higher than that of the uncatalyzed reaction (Table 1, entry 2 vs. entry 1), which suggests that ODN-1 might function as an enantioselective catalyst for the D-A reaction.We assembled a complex between Cu(NO 3 ) 2 and ODN-1 (ODN-1-Cu 2+ ) and tested its ability to enantioselectively catalyze the D-A reaction. ODN-1-Cu 2+ provides a significant enhancement in the reaction rate ( entry 3). We also observed an excellent diastereoselectivity for product 3 a (endo/exo of 98:2) and a good enantioselectivity (74 % ee). These results suggest that ODN-1-Cu 2+ can serve as a potent catalyst, providing stereoselectivity and enhancement in reaction rates. To furthe...

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Enantioselective Friedel–Crafts reactions in water catalyzed by a human telomeric G-quadruplex DNA metalloenzyme

Cited by 116 publications

References 44 publications

DNA-based asymmetric catalysis: role of ionic solvents and glymes

DNA-based asymmetric catalysis: role of ionic solvents and glymes

Enantioselective Diels–Alder Reactions with G‐Quadruplex DNA‐Based Catalysts

Enantioselective Diels–Alder Reactions with G‐Quadruplex DNA‐Based Catalysts

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