Artificial G-quadruplex DNA metalloenzyme and application thereof

A quadruplex and metalloenzyme technology, applied in the field of artificial G-quadruplex DNA metalloenzyme, can solve the problem of low ee%, and achieve the effects of simple operation, mild reaction conditions and good enantioselectivity

Active Publication Date: 2021-10-12
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 2016, Gerard Roelfes group used a DNA-based catalyst (salmon testis DNA, a double-stranded DNA) to catalyze the cyclopropanation reaction of p-methylstyrene, but the obtained ee% was relatively low, only about 50%

Method used

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  • Artificial G-quadruplex DNA metalloenzyme and application thereof
  • Artificial G-quadruplex DNA metalloenzyme and application thereof
  • Artificial G-quadruplex DNA metalloenzyme and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053] Add potassium phosphate (KPi) buffer solution (10mM, pH 7.0) to a 10mL Schlenk tube with a stirring bar, argon for 10min, add DNA (12.5μM): GGTTGGTGTGGTTGG (TBA), under the protection of argon (bubbling , open to the atmosphere), then add FeTMPyP4 (12.5μM), and stir for 10min to generate artificial G-quadruplex DNA metalloenzyme in situ (see figure 1 and figure 2 ), the ratio of artificial G-quadruplex DNA to FeTMPyP4 is 1:1. Sodium dithionite (5mM), styrene (30mM) and ethyl diazoacetate (10mM) were added to the above system, reacted and stirred for 2h at 4°C, and the reaction was terminated, extracted with ethyl acetate, and the product (1RS , 2RS)-2-phenylcyclopropane-1-carboxylic acid ethyl ester [(1RS,2RS)-Ethyl 2-phenylcyclopropane-1-carboxylate], the product is separated and detected by chiral high-performance liquid chromatography, and the chiral column uses OJH column. Analytical results: 48% enantioselectivity.

[0054] Product analysis

[0055] 1:10), t...

Embodiment 2

[0057] Add potassium phosphate (KPi) buffer solution (10mM, pH 7.0) to a 10mL Schlenk tube with a stirring bar, argon for 10min, add DNA (12.5μM): TGGTCGGTGTGGTTGGT (TmC4T), under argon protection (bubbling , open to the atmosphere), then add FeTMPyP4 (12.5μM), and stir for 10min to generate artificial G-quadruplex DNA metalloenzyme in situ (see figure 1 and figure 2 ), the ratio of artificial G-quadruplex DNA to FeTMPyP4 is 1:1. Add sodium dithionite (5mM), styrene (30mM) and ethyl diazoacetate (10mM) to the above system, react and stir for 2h at 4°C, then end the reaction, extract with ethyl acetate, and obtain the product (1RS , 2RS)-2-phenylcyclopropane-1-carboxylic acid ethyl ester [(1RS,2RS)-Ethyl 2-phenylcyclopropane-1-carboxylate], the product is separated and detected by chiral high-performance liquid chromatography, and the chiral column uses OJH column. Analytical results: -79% enantioselectivity.

[0058] Product analysis

[0059] 1:10), to afford the produ...

Embodiment 3

[0061] Add potassium phosphate (KPi) buffer solution (10mM, pH 7.0) to a 10mL Schlenk tube with a stirring bar, argon for 10min, add DNA (12.5μM): TGGTCGGTGTGGTTGGT (TmC4T), under argon protection (bubbling , open to the atmosphere), then add FeTMPyP4 (25μM), stir for 10min to generate artificial G quadruplex DNA metalloenzyme in situ, the ratio of artificial G quadruplex DNA and FeTMPyP4 is 1:2. Add sodium dithionite (5mM), styrene (30mM) and ethyl diazoacetate (10mM) to the above system, react and stir for 2h at 4°C, then end the reaction, extract with ethyl acetate, and obtain the product (1RS , 2RS)-2-phenylcyclopropane-1-carboxylic acid ethyl ester [(1RS,2RS)-Ethyl 2-phenylcyclopropane-1-carboxylate], the product is separated and detected by chiral high-performance liquid chromatography, and the chiral column uses OJH column. Analytical results: -73% enantioselectivity.

[0062] Product analysis

[0063] Purified by column chromatography (SiO 2 , EtOAc:pentane=1:10)...

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Abstract

The invention discloses an artificial G-quadruplex DNA metalloenzyme and application thereof. The metalloenzyme consists of ferriporphyrin and artificial G-quadruplex DNA. In the presence of K < + >, the artificial G-quadruplex DNA and ferriporphyrin are mixed in a buffer solution, and the artificial G-quadruplex DNA metalloenzyme can be obtained through in-situ synthesis by stirring. When the artificial G-quadruplex metalloenzyme is applied to olefin asymmetric cyclopropanation reaction, the artificial G-quadruplex metalloenzyme shows relatively high catalytic activity and relatively high selectivity. The artificial G-quadruplex DNA metalloenzyme does not contain precious metal components, the reaction cost is remarkably reduced, and the artificial G-quadruplex DNA metalloenzyme is mild in use condition and is a novel artificial enzyme which is environmentally friendly, high in activity, high in selectivity and excellent in stability.

Description

technical field [0001] The invention relates to a catalytically active artificial DNA metalloenzyme, in particular to an artificial G quadruplex DNA metalloenzyme, which is suitable for catalyzing the asymmetric cyclopropanation reaction of alkenes. Background technique: [0002] Transition metal-catalyzed carbene transfer reactions are a powerful approach to functionalize C=C and C–H bonds. DNA-based catalysis is to combine metal compounds into the DNA molecular framework. DNA provides a second coordination environment and provides a chiral environment for the reaction substrate, thereby improving the selectivity of the reaction and accelerating the reaction rate at the same time. [0003] The traditional cyclopropanation reaction is mainly realized by Simmons-Smith reaction, but this method usually requires the use of organic solvents, chiral auxiliary agents for resolution or chiral additives and other disadvantages. [0004] [0005] Patent CN 110041361A discloses a ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22C07C67/347C07C69/753
CPCB01J31/183C07C67/347B01J2531/842B01J2531/025B01J2231/325C07C2601/02C07C69/753
Inventor 李灿郝静雅苗文慧
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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