4.7 Article

Coordinative Alignment of Chiral Molecules to Control over the Chirality Transfer in Spontaneous Resolution and Asymmetric Catalysis

Journal

SCIENTIFIC REPORTS
Volume 7, Issue -, Pages -

Publisher

NATURE PUBLISHING GROUP
DOI: 10.1038/s41598-017-15780-0

Keywords

-

Funding

  1. National Natural Science Foundation of China [U1608224, 21421005, 21231003]

Ask authors/readers for more resources

The production and availability of enantiomerically pure compounds that spurred the development of chiral technologies and materials are very important to the fine chemicals and pharmaceutical industries. By coordinative alignment of enantiopure guests in the metal. organic frameworks, we reported an approach to control over the chirality of homochiral crystallization and asymmetric transformation. Synthesized by achiral triphenylamine derivatives, the chirality of silver frameworks was determined by the encapsulated enantiopure azomethine ylides, from which clear interaction patterns were observed to explore the chiral induction principles. With the changing of addition sequence of substrates, the enantioselectivity of asymmetric cycloaddition was controlled to verify the determinant on the chirality of the bulky MOF materials. The economical chirality amplification that merges a series of complicated self-inductions, bulk homochiral crystallization and enantioselective catalysis opens new avenues for enantiopure chemical synthesis and provides a promising path for the directional design and development of homochiral materials.

Authors

I am an author on this paper
Click your name to claim this paper and add it to your profile.

Reviews

Primary Rating

4.7
Not enough ratings

Secondary Ratings

Novelty
-
Significance
-
Scientific rigor
-
Rate this paper

Recommended

Article Nanoscience & Nanotechnology

Ir-Porphyrin-Based Metal-Organic Framework as a Dual Metallo- and Photocatalyst for Inert Alkyl C(sp3)-H Bond Activation and Direct Functionalization

Yefei Wang, Zhen Zhou, Liang Zhao, Cheng He, Wenlong Sun, Chunying Duan

Summary: By stabilizing highly active carbenes in metal-organic frameworks, efficient acceleration of carbene migratory insertion and C-H bond activation was achieved, leading to inert alkane functionalization. The first-time isolation and structural characterization of Ir-III-carbene intermediates were successfully conducted.

ACS APPLIED MATERIALS & INTERFACES (2021)

Article Multidisciplinary Sciences

A host-guest semibiological photosynthesis system coupling artificial and natural enzymes for solar alcohol splitting

Junkai Cai, Liang Zhao, Cheng He, Yanan Li, Chunying Duan

Summary: The study develops a novel coenzyme-mediated supramolecular host-guest semibiological system integrating artificial and enzymatic catalysis for photocatalytic hydrogen evolution. This approach enables effective proton reduction inside the artificial host, paving a unique avenue for synergic combination of abiotic and biotic synthetic sequences in photocatalytic fuel and chemical transformation.

NATURE COMMUNICATIONS (2021)

Article Nanoscience & Nanotechnology

Vanadium(VIV)-Porphyrin-Based Metal-Organic Frameworks for Synergistic Bimetallic Activation of Inert C(sp3)-H Bonds

Yefei Wang, Liang Zhao, Guanfeng Ji, Cheng He, Songtao Liu, Chunying Duan

Summary: In this study, the inert C(sp(3))-H bond activation was achieved by stabilizing the active tertbutyl peroxide radical with vanadium(V-IV)-porphyrin-based metal-organic frameworks (MOFs) and utilizing a synergistic bimetallic strategy via a hydrogen atom transfer process. The introduction of {Mn-3(mu(3)-O)} cluster nodes into MOFs resulted in the pre-activation of substrates, leading to enhanced conversion efficiency and product selectivity for inert C(sp(3))-H bond functionalization.

ACS APPLIED MATERIALS & INTERFACES (2022)

Article Chemistry, Multidisciplinary

A Metal-Organic Framework as a Multiphoton Excitation Regulator for the Activation of Inert C(sp3)-H Bonds and Oxygen

Guanfeng Ji, Liang Zhao, Jianwei Wei, Junkai Cai, Cheng He, Zenggang Du, Wei Cai, Chunying Duan

Summary: The article introduces a novel multiphoton excitation approach to activate inert C(sp(3))-H bonds and oxygen, which enables oxidation reactions and the development of sustainable synthetic strategies through integration of various events.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

Article Chemistry, Inorganic & Nuclear

Eosin Y-Containing Metal-Organic Framework as a Heterogeneous Catalyst for Direct Photoactivation of Inert C-H Bonds

Liang Zhao, Zenggang Du, Guanfeng Ji, Yefei Wang, Wei Cai, Cheng He, Chunying Duan

Summary: Decorating eosin Y into a porous metal-organic framework (MOF) enhances the chemical durability and activates inert C-H bonds by forming excited state radicals, thus improving reaction efficiency. This novel heterogeneous photocatalytic system provides a feasible catalytic avenue for the practical application of organic dyes.

INORGANIC CHEMISTRY (2022)

Article Chemistry, Inorganic & Nuclear

Anthraquinone-Based Metal-Organic Frameworks as a Bifunctional Photocatalyst for C-H Activation

Liang Zhao, Wei Cai, Guanfeng Ji, Jianwei Wei, Zenggang Du, Cheng He, Chunying Duan

Summary: This study reports an anthraquinone-based metal-organic framework (MOF) as a bifunctional photocatalytic platform to simultaneously activate inert C-H bonds and oxygen for C-H bond oxidation. The MOF exhibits great chemical stability and synergistic photocatalytic effects. The platform can efficiently oxidize substrates containing benzylic C(sp(3))-H bonds under visible light irradiation.

INORGANIC CHEMISTRY (2022)

Article Chemistry, Physical

A Binuclear Cerium-Based Metal-Organic Framework as an Artificial Monooxygenase for the Saturated Hydrocarbon Aerobic Oxidation with High Efficiency and High Selectivity

Guanfeng Ji, Liang Zhao, Yefei Wang, Yang Tang, Cheng He, Songtao Liu, Chunying Duan

Summary: An artificial binuclear cerium monooxygenase catalyst with high selectivity and activity for oxidation of inert C-H bonds was obtained by constructing a metal-organic framework (MOF) with active sites similar to natural enzymes. The MOF exhibited a unique catalytic performance and could be recycled without loss of selectivity and activity, providing a blueprint for designing new artificial monooxygenase for inert alkane oxidation.

ACS CATALYSIS (2022)

Article Chemistry, Multidisciplinary

Light-switched selective catalysis with NADH mimic functionalized metal-organic capsules

Jianwei Wei, Liang Zhao, Yu Zhang, Peng Zhou, Guangzhou Liu, Chunying Duan

Summary: By incorporating an active site model of nicotinamide adenine dinucleotide (NADH) as an electron regulator, a highly efficient photocatalyst was synthesized for the light switchable synthesis of aromatic azoxy and amino compounds from nitroaromatics under purple or blue LED light irradiation.

CHEMICAL COMMUNICATIONS (2022)

Article Nanoscience & Nanotechnology

Mixed-Component Metal-Organic Framework for Boosting Synergistic Photoactivation of C(sp3)-H and Oxygen

Yefei Wang, Liang Zhao, Songtao Liu, Guanfeng Ji, Cheng He, Yang Tang, Chunying Duan

Summary: Synergistic catalysis is an efficient strategy for activating reactants by multiple active sites. Metal-organic frameworks (MOFs) with multiple active sites have attracted interest as heterogeneous catalytic platforms. Here, we report a MOF with dual active sites, which can simultaneously activate inert C(sp3)-H bonds for oxidation under mild conditions.

ACS APPLIED MATERIALS & INTERFACES (2023)

Article Chemistry, Multidisciplinary

Enzyme Grafting with a Cofactor-Decorated Metal-Organic Capsule for Solar-to-Chemical Conversion

Jianwei Wei, Liang Zhao, Yu Zhang, Gang Han, Cheng He, Chong Wang, Chunying Duan

Summary: An enzyme grafting strategy was used to create a metal-organic capsule-docking artificial enzyme that bypasses the need for cofactor shuttling and regeneration. This semi-artificial enzyme efficiently converts various types of alcohols to amine products in aqueous/organic solutions and Escherichia coli, offering opportunities for sustainable and environmentally friendly biomanufacturing.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2023)

Article Materials Science, Multidisciplinary

Dye-Binding Metal-Organic Cage for Highly Efficient Multiphoton Activation of C(sp 3)-H Bonds

Yu Zhang, Liang Zhao, Jianwei Wei, Guanfeng Ji, Huali Wang, Cheng He, Lehua Zhao, Chunying Duan

Summary: This study presents a new Ce-III-based octahedral cage that enhances C(sp(3))-H photoactivation by combining a Ce-IV-Cl photocatalyst and a photoredox catalyst. It integrates photoinduced electron transfer, ligand-to-metal charge transfer, and hydrogen-atom transfer through multiphoton excitation. The cage binds to 2-chloro-9H-thioxanthen-9-one, boosting PET and enabling the oxidation of Ce-III-Cl to Ce-IV-Cl, resulting in the formation of highly electrophilic radicals similar to enzymes.

ACS MATERIALS LETTERS (2023)

Article Chemistry, Inorganic & Nuclear

Ligand-regulated photoinduced electron transfer within metal-organic frameworks for efficient photocatalysis

Yang Tang, Guanfeng Ji, Hanning Li, Hui Gao, Cheng He, Liang Zhao, Chunying Duan

Summary: A new method is reported to control the direction of photoinduced electron transfer (PET) in dye-based metal-organic frameworks (MOFs) by introducing a carbonyl group into triphenylamine to form an acridone ligand. Through solvothermal reaction, a new acridone-based Co-MOF was fabricated and found to inhibit intramolecular PET process, leading to efficient photocatalytic organic transformations. This new heterogeneous platform provides a promising approach to modulate PET direction in MOFs and develop multipurpose and flexible catalytic systems.

INORGANIC CHEMISTRY FRONTIERS (2023)

Article Chemistry, Multidisciplinary

Binding of Dual-Function Hybridized Metal-Organic Capsules to Enzymes for Cascade Catalysis

Junkai Cai, Liang Zhao, Yanan Li, Cheng He, Chong Wang, Chunying Duan

Summary: The combination of chemo-and biocatalysis provides advantages in multistep syntheses. This study presents a progressive host-guest strategy to mimic cytochrome P450s catalysis using encapsulated flavin analogues in metal-organic capsules. The strategy involves multistage directional electron flow and offers selective conversion of stilbene to oxidative coupling products in tandem with enzymatic reactions.

JACS AU (2022)

Article Chemistry, Inorganic & Nuclear

Ligand-regulated metal-organic frameworks for synergistic photoredox and nickel catalysis

Yang Tang, Liang Zhao, Guanfeng Ji, Yu Zhang, Cheng He, Yefei Wang, Jianwei Wei, Chunying Duan

Summary: Synergistic photoredox and nickel catalytic cross-coupling systems have attracted attention as a promising method for the synthesis of C-N bonds under mild conditions. However, these systems face challenges from photoinduced electron transfer. This study successfully overcame this challenge by controlling the geometry configuration of ligands and constructing a hybrid material with unique electronic conductivity characteristics in metal-organic frameworks.

INORGANIC CHEMISTRY FRONTIERS (2022)

Article Chemistry, Physical

A Binuclear Cerium-Based Metal-Organic Framework as an Artificial Monooxygenase for the Saturated Hydrocarbon Aerobic Oxidation with High Efficiency and High Selectivity

Guanfeng Ji, Liang Zhao, Yefei Wang, Yang Tang, Cheng He, Songtao Liu, Chunying Duan

Summary: A new metal-organic framework supported artificial binuclear cerium monooxygenase was successfully synthesized and used for the highly selective oxidation of inert C-H bond substrates. This artificial enzyme exhibited unique catalytic selectivity and high activity, providing a new blueprint for designing new artificial enzymes for the oxidation of inert alkanes.

ACS CATALYSIS (2022)

No Data Available