Article
Chemistry, Multidisciplinary
Linlong Dai, Yuheng Liu, Qing Xu, Meifang Wang, Qiaohong Zhu, Peiyuan Yu, Guofu Zhong, Xiaofei Zeng
Summary: This paper presents a dynamic kinetic resolution method for the synthesis of axially chiral diaryl ethers. By using a Bronsted acid catalyzed atroposelective transfer hydrogenation (ATH) reaction, the desired diaryl ethers could be obtained in moderate to good chemical yields (up to 79%) and high enantioselectivities (up to 95% ee) under standard reaction conditions. These structural motifs are interesting precursors for further transformations and may have potential applications in the synthesis of chiral ligands or catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Hong-Hao Zhang, Tian-Zhen Li, Si-Jia Liu, Feng Shi
Summary: The catalytic asymmetric synthesis of atropisomers bearing multiple chiral elements has recently become an emerging research field. Chemists have devised metal-catalyzed or organocatalytic asymmetric reactions for accessing atropisomers with multiple chiral elements, such as those with center chirality, planar chirality, and helical chirality. This review summarizes the rapid developments in this field and indicated the remaining challenges.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yan-Bo Li, Hu Tian, Shuai Zhang, Jun-Zhao Xiao, Liang Yin
Summary: In this study, a copper(I)-catalyzed reaction of diarylphosphines and O-benzoyl hydroxylamines was developed, leading to the synthesis of aminophosphinites and P-chiral aminophosphinites. The reaction mechanism was proposed and further transformation to P-chiral phosphines was achieved.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Patricia Rodriguez-Salamanca, Gonzalo de Gonzalo, Jose A. Carmona, Joaquin Lopez-Serrano, Javier Iglesias-Siguenza, Rosario Fernandez, Jose M. Lassaletta, Valentin Hornillos
Summary: This article describes a highly enantioselective biocatalytic dynamic kinetic resolution (DKR) for configurationally labile N-arylindole aldehydes. The DKR is achieved through atroposelective bioreduction of the carbonyl group using commercial ketoreductases (KREDs), resulting in axially chiral N-arylindole aminoalcohols with excellent conversions and optical purities. The strategy relies on the racemization of the stereogenic axis facilitated by a transient Lewis pair interaction between NMe2 and the aldehyde groups. This protocol offers a broad substrate scope under mild conditions.
Article
Chemistry, Physical
Jose A. Carmona, Carlos Rodriguez-Franco, Joaquin Lopez-Serrano, Abel Ros, Javier Iglesias-Siguenza, Rosario Fernandez, Jose M. Lassaletta, Valentin Hornillos
Summary: An efficient dynamic kinetic resolution (DKR) approach has been developed for the synthesis of axially chiral diamines based on ruthenium-catalyzed enantioselective transfer hydrogenation. This method features a broad substrate scope and proceeds under very mild conditions, allowing the preparation of BINAM homologues in good to high yields and nearly perfect enantioselectivities (up to 99% ee).
Review
Chemistry, Applied
Giovanni Maria Fusi, Silvia Gazzola, Umberto Piarulli
Summary: Transition metal chiral catalysts can have metal stereocenters in different coordination geometries, with stability achieved through the use of multidentate ligands or cyclopentadienyl anions to prevent decomplexation and recomplexation of labile ligands, allowing for highly enantioselective reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Review
Chemistry, Organic
Mengyao Tang, Xiaoyu Yang
Summary: Inherent chirality is a distinct form of molecular chirality that does not fit into the traditional classification of four chiral elements. This article provides a comprehensive summary of recent advancements in the catalytic asymmetric synthesis of inherently chiral molecules, including chiral calixarenes, saddle-shaped chiral cycles, and mechanically planar chiral rotaxanes.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yang-Bo Chen, Li-Gao Liu, Can-Ming Chen, Yi-Xi Liu, Bo Zhou, Xin Lu, Zhou Xu, Long-Wu Ye
Summary: In this study, a copper-catalyzed atroposelective diyne cyclization was disclosed for the synthesis of a range of axially chiral arylpyrrole biaryls with good to excellent yields and enantioselectivities. This method represents the first synthesis of mono-substituted 3-arylpyrrole atropisomers and the first example of atroposelective diyne cyclization and atropisomer construction using vinyl cations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Ramon de la Serna, Joaquin Perez-Pariente, Luis Gomez-Hortigueela
Summary: In this study, the asymmetric catalytic activity of GTM-3 chiral zeolite in the ring-opening reaction of trans-stilbene oxide using alcohols as nucleophiles was systematically explored. The results showed that a proper chiral host-guest size match is crucial for the chiral manifestation of the zeolite catalyst. Additionally, secondary alcohols with larger size exhibited higher enantioselectivity than their linear counterparts. Furthermore, variation of reaction conditions, such as the concentration of the epoxide and reaction temperature, could greatly influence the enantioselectivity and selectivity of the reaction.
Article
Chemistry, Applied
Hong-Xin Jiang, Dan-Dan Han, Rui-Ping Song, Qin Shi, Xiao-Fan He, Wan-Qing Kou, Qi Zhao, You-Dong Shao, Dao-Juan Cheng
Summary: Here, a chiral boro-phosphate catalyst is presented for an atroposelective asymmetric transfer hydrogenation method, allowing the synthesis of axially chiral styrene-type allyl alcohols. This dynamic kinetic resolution approach offers a simple procedure, mild conditions, and good enantiocontrol (51-95% ee), providing an important alternative for constructing challenging atropisomeric aryl-acyclic alkene scaffolds.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Masamichi Ogasawara
Summary: Planar-chiral transition metal complexes are important in asymmetric synthesis, but their preparation remains challenging. Reported examples of catalytic enantioselective synthesis of planar-chiral complexes are rare and represent a developing area in this field.
Article
Chemistry, Physical
Zeng Gao, Chao-Xian Yan, Jinlong Qian, Huameng Yang, Panpan Zhou, Jinlong Zhang, Gaoxi Jiang
Summary: An efficient and rapid method for constructing a family of axially chiral sulfonamides with a wide functional group tolerance has been developed through Pd-catalyzed atroposelective hydroamination. Simple oxidation and gamma-addition enabled the synthesis of various valuable axially chiral sulfonamides and anilides, including non-natural amino acid derivatives. Preliminary DFT calculations were used to explain the origin of asymmetric induction.
Article
Chemistry, Multidisciplinary
Jose A. Carmona, Patricia Rodriguez-Salamanca, Rosario Fernandez, Jose M. Lassaletta, Valentin Hornillos
Summary: An atroposelective Ir-catalyzed dynamic kinetic resolution (DKR) of 2-(quinolin-8-yl)benzaldehydes/1-naphthaldehydes is achieved by transfer hydrogenative coupling of allyl acetate. The reaction leads to the installation of central and axial chirality, with high diastereoselectivities and excellent enantioselectivities when ortho-cyclometalated iridium-DM-BINAP is used as the catalyst. The racemization of the substrates is facilitated through a designed transient Lewis acid-base interaction between the quinoline nitrogen atom and the aldehyde carbonyl group.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Chenghua Deng, Bai-Qiao Song, Matteo Lusi, Andrey A. Bezrukov, Molly M. Haskins, Mei-Yan Gao, Yun-Lei Peng, Jian-Gong Ma, Peng Cheng, Soumya Mukherjee, Michael J. J. Zaworotko
Summary: A new chiral metal-organic material, CMOM-5, has been developed to design chiral crystalline sponges and determine the crystal structures of liquid enantiomers. CMOMs can mimic the enantioselectivity of biomolecules and can be fine-tuned for structure and properties. CMOM-5, composed of rod building blocks and bipy linkers, can adapt its pore structure to bind different guest molecules, exhibiting chiral resolution with high enantiomeric excess values. The flexibility of CMOM-5 allows the determination of eight enantiomeric crystal structures, including the first crystal structures of R-4P2B, S-4P2B, and R-MPE ambient liquids.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Multidisciplinary
Lenka Pallova, Laura Abella, Marion Jean, Nicolas Vanthuyne, Cecile Barthes, Laure Vendier, Jochen Autschbach, Jeanne Crassous, Stephanie Bastin, Vincent Cesar
Summary: The first efficient chiral helicene-NHC gold(I) complexes for enantioselective catalysis have been synthesized. Their structural and stereochemical characterization confirms their potential in asymmetric catalysis, demonstrated by the benchmark cycloisomerization reaction with high enantiomeric excess.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Nanoscience & Nanotechnology
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
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
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
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
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
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
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.
Article
Chemistry, Multidisciplinary
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
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
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
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
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
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.
Article
Chemistry, Inorganic & Nuclear
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
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.