Article
Chemistry, Multidisciplinary
Amarajothi Dhakshinamoorthy, Abdullah M. Asiri, Hermenegildo Garcia
Summary: This article discusses the potential of metal-organic frameworks (MOFs) in heterogeneous catalysis as frustrated Lewis acid-base pairs (FLPs) or bifunctional acid-base solid catalysts for activating molecular hydrogen. Specifically, it focuses on the use of MOFs as Lewis acid and Lewis base catalysts, and the efforts to heterogenize boron and amine in MOFs to mimic molecular FLP systems. The article highlights the catalytic hydrogenation capabilities of UiO-66 and MIL-101 MOFs and their significance in selectively hydrogenating polar double X=Y bonds.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Christoph Wallach, Felix S. Geitner, Antti J. Karttunen, Thomas F. Faessler
Summary: The unique three-dimensional structure of spherical, homoatomic nine-atom germanium clusters allows for various spatial arrangement of functional groups. Recent introduction of ligands with lone pairs and addition of boranyl group to the cluster featuring a Ge-B exo-cluster bond have expanded the possibilities in cluster chemistry. Quantum-chemical calculations have revealed the frustrated Lewis pair character of the boranyl-functionalized cluster.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Joshua S. Sapsford, Daniel Csokas, Roland C. Turnell-Ritson, Liam A. Parkin, Andrew D. Crawford, Imre Papai, Andrew E. Ashley
Summary: The newly synthesized compound iPr(3)SnNTf(2) exhibits stronger Lewis acid properties compared to previously studied compounds, enabling faster hydrogen activation and catalytic hydrolysis of ester bonds. The reaction outcome is influenced by the steric and electronic properties of the substrate, with computational studies revealing differences in the reaction mechanisms between different ester substrates.
Review
Biochemistry & Molecular Biology
Qiang Wan, Sen Lin, Hua Guo
Summary: This article reviews recent theoretical advances in understanding FLP-based heterogeneous catalysis in various applications, such as metal oxides, functionalized surfaces, and two-dimensional materials. It emphasizes the importance of a better understanding of the catalytic mechanism for the experimental design of novel heterogeneous FLP catalysts.
Article
Chemistry, Multidisciplinary
Yan Liang, Zhong Zhang, Xiaofang Su, Xiao Feng, Songzhu Xing, Wei Liu, Rui Huang, Yiwei Liu
Summary: Precisely controlling the structure and spatial distance between Lewis acid and Lewis base sites in a porous system is essential for constructing efficient solid frustrated Lewis pair (FLP) catalysts. In this study, FLP sites were constructed in a polyoxometalate (POM)-based metal-organic framework (MOF) by introducing coordination-defect metal nodes (Lewis acid) and surface-basic POM with abundant oxygen (Lewis base). The resulting FLP catalyst exhibited high hydrogenation activity, with 55 and 2.7 times higher activity compared to defect-free POM-based MOF and defective MOF without POM, respectively. This work offers a new approach for the precise design of multi-site catalysts for specific substrate activation and synergistic catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Shubhajit Das, Roland C. Turnell-Ritson, Paul J. Dyson, Clemence Corminboeuf
Summary: Despite recent progress in the chemistry of frustrated Lewis pairs (FLPs), direct FLP-catalyzed hydrogenation of CO2 remains elusive. The authors propose a mapping method to link the chemical composition of FLPs with their activity in catalytic hydrogenation of CO2, and they experimentally validate a combination with high catalytic turnover.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Felix Wech, Urs Gellrich
Summary: This review discusses the hydrogenation of organic substrates catalyzed by borane-based frustrated Lewis pairs, with a focus on the mechanistic aspects of these catalytic reactions.
SYNTHESIS-STUTTGART
(2022)
Review
Chemistry, Multidisciplinary
Minsoo Ju, Zhipeng Lu, Luiz F. T. Novaes, Jesus I. Martinez Alvarado, Song Lin
Summary: Frustrated radical pairs (FRPs) are able to coexist in solution due to steric repulsion or weak bonding association between two distinct radicals, which would otherwise annihilate each other. They are typically formed via spontaneous single-electron transfer between two sterically encumbered precursors and exhibit orthogonal chemical properties. FRPs have been found to be capable of homolytically activating various chemical bonds and are being extensively explored in synthetic organic chemistry, including C-H bond functionalization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Ranita Pal, Manas Ghara, Pratim Kumar Chattaraj
Summary: This article provides a review of the chemistry of frustrated Lewis pair (FLP) in the activation of small molecules, hydrogenation of CO2, and unsaturated organic species. Experimental works and electronic structure theory calculations are used to gain mechanistic insights into the reactivity of FLPs. The findings can guide the design of more efficient FLP catalysts for hydrogen activation.
Article
Chemistry, Multidisciplinary
Xinyue Tan, Huadong Wang
Summary: The concept of frustrated Lewis pair (FLP) chemistry has become a rich and fruitful research area, contributing significantly to the revival of main group chemistry. The design of catalytic systems based on the FLP concept has been successfully applied to organic synthesis and polymer chemistry.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Physical
Hui Mao, Zijiang Chen, Longjiu Cheng, Kun Wang
Summary: The article discusses the catalytic effect and hydrogen storage potential of Frustrated Lewis Pairs (FLPs) in the hydrogenation process, emphasizing the influence of acidity and alkalinity on the activity and reversibility of FLPs. The study found that FLPs composed of strong acids and relatively weak bases exhibit better reversibility and reaction rates in hydrogenation.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2021)
Review
Biochemical Research Methods
Gitanjali Sharma, Paul D. Newman, James A. Platts
Summary: This review discusses the power of quantum chemistry, particularly density functional theory (DFT), in unraveling mechanisms in the field of FLP chemistry. It covers various aspects such as hydrogen activation, borylation, silylation, polymerization, formation of heterocycles, reaction with small gaseous molecules, alkenes, terminal alkynes, and the role of DFT in understanding regio-selectivity, steric effects, London dispersion, and covalent interactions in FLPs.
JOURNAL OF MOLECULAR GRAPHICS & MODELLING
(2021)
Article
Chemistry, Multidisciplinary
Tongtong Wang, Maotong Xu, Andrew R. Jupp, Zheng-Wang Qu, Stefan Grimme, Douglas W. Stephan
Summary: The frustrated Lewis pair (FLP) derived from 2,6-lutidine and B(C6F5)(3) has been shown to mediate the catalytic hydrogenation of CO2, with control over product nature through careful selection of silylhalide and solvent. This metal-free catalysis offers pathways to selectively form specific compounds under mild conditions, as elucidated by DFT studies on the mechanism and selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jorge Juan Cabrera-Trujillo, Israel Fernandez
Summary: The presence of cyclopropenimine moiety in geminal frustrated Lewis pairs enhances the reactivity of the system towards small molecule activation by increasing the aromaticity strength of this fragment, leading to low energy barriers and high exergonic transformations.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Haishuai Cui, Xiaoqing Liao, Yufan Ren, Yang Zhou, Jing Xiao, Renjie Deng, Yang Lv, Huajie Liu, Pingle Liu, Hai Yang
Summary: In this article, a facile strategy is proposed to synthesize oxygen-defect-rich Co3O4@NC porous nanorods. These materials are proven to have FLPs sites. The oxygen-defect-rich Co3O4@NC exhibits high selectivity and catalytic performance towards cinnamaldehyde.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Organic
Qing-Xian Xie, Li-Xia Liu, Zhou-Hao Zhu, Chang-Bin Yu, Yong-Gui Zhou
Summary: In this study, a ruthenium-catalyzed asymmetric transfer hydrogenation of 2,3-disubstituted flavanones was developed. The reaction allowed for the construction of three contiguous stereocenters under basic conditions through a combination of dynamic kinetic resolution and retro-oxa-Michael addition. This method provided chiral flavanols with excellent enantioselectivities and diastereoselectivities.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Zilong Huang, Yuan He, Liandi Wang, Jiying Li, Bao-Hua Xu, Yong-Gui Zhou, Zhengkun Yu
Summary: A concise synthetic route to spiroindoline-fused S-heterocycles was developed using copper-catalyzed [4 + 1] annulation and enaminothiones as donor-acceptor synthons. The reaction showed good reactivity, broad substrate tolerance, and high yields.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Xin-Wei Wang, Wen-Jun Huang, Han Wang, Bo Wu, Yong-Gui Zhou
Summary: In this study, a catalytic asymmetric Pictet-Spengler reaction on the benzene ring of indoles was achieved using chiral phosphoric acid, resulting in the synthesis of polycyclic indole derivatives with Spiro quaternary stereocenters in excellent yields and enantioselectivities. The reaction could be conducted on a gram scale without any loss of activity or enantioselectivity.
Article
Chemistry, Applied
Yuan He, Zilong Huang, Juan Ma, Jie Lin, Yong-Gui Zhou, Zhengkun Yu
Summary: A transition-metal-free method was developed for the cleavage of C-H bonds in olefins. By using vinylsulfonium salts and sodium azide, sulfanyl-azidoalkene compounds were synthesized and further transformed into various derivatives.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Yi-Xuan Ding, Zhou-Hao Zhu, Mu-Wang Chen, Chang-Bin Yu, Yong-Gui Zhou
Summary: In this study, the asymmetric hydrogenation of all-carbon aromatic rings was achieved using rhodium/diphosphine catalysts. The introduction of chiral diphosphine ligands with steric hindrance and strong electron-donating properties was key to the success in obtaining axially chiral cyclic compounds with high enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Xiao-Qing Wang, Bo Wu, Yu-Qing Bai, Xiao-Yong Zhai, Yong-Gui Zhou
Summary: This study presents an easy-to-operate and efficient CuH-catalyzed consecutive asym-metric hydrosilylation/dehydrocoupling polymerization method for synthesizing chiral poly(silyl ether)s. The method offers advantages such as atom economy, broad substrate scope, and high stereoselectivity.
EUROPEAN POLYMER JOURNAL
(2022)
Article
Chemistry, Organic
Kun Wang, Yan-Jiang Yu, Xiao-Qing Wang, Yu-Qing Bai, Mu-Wang Chen, Yong-Gui Zhou
Summary: In this study, a palladium-catalyzed asymmetric hydrogenation of unprotected 3-substituted indoles was developed, providing a series of 3-substituted indolines in high yields with good enantioselectivity (<= 94.4:5.6 er). The bulky bisphosphine ligand played a crucial role in controlling the enantioselectivity. In addition, gram-scale hydrogenation experiments and product derivatizations were successfully conducted.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Polymer Science
Xiao-Qing Wang, Yu-Qing Bai, Kun Wang, Bo Wu, Yong-Gui Zhou
Summary: This paper presents a metal-free insertion polymerization method for constructing carbon-heteroatom bonds in the main chain. Sulfoxonium ylides are used as monomers to produce polythioethers and aromatic polyamines with high yield and molecular weight. The method features mild conditions, easy operation, and a wide range of substrate applicability.
EUROPEAN POLYMER JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Xiang Li, Gao-Wei Wang, Li-Xia Liu, Chang-Bin Yu, Yong-Gui Zhou
Summary: Here, the authors describe the first example of palladium-catalyzed asymmetric hydrogenolysis of easily accessible aryl triflates for the construction of axially chiral biaryl scaffolds. The resulting chiral biaryl compounds were used to prepare axially chiral monophosphine ligands, which were further employed in palladium-catalyzed asymmetric allylic alkylation with excellent enantioselectivities and high branched and linear ratios, highlighting the potential utility of this methodology.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Tong Niu, Li-Xia Liu, Bo Wu, Yong-Gui Zhou
Summary: A series of [2,2]paracyclophane-based tridentate PNO ligands with planar chirality were designed and synthesized. These easily prepared chiral tridentate PNO ligands were successfully applied to the iridium-catalyzed asymmetric hydrogenation of simple ketones, providing chiral alcohols with high efficiency and excellent enantioselectivities (up to 99% yield and >99% ee). Control experiments demonstrated the indispensability of both N-H and O-H in the ligands.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Zilong Huang, Jie Lin, Mingrui Li, Zhengkun Yu, Yong-Gui Zhou
Summary: A zinc(II)-catalyzed [2+2+1] annulation reaction of internal alkenes, diazooxindoles, and isocyanates was developed for the efficient synthesis of multisubstituted spirooxindoles. This multi-component transformation involves the in situ formation of a sulfur-containing spirocyclic intermediate, followed by a 1,3-dipolar addition reaction of the intermediate with the internal alkene, resulting in a formal [2+2+1] annulation in a one-pot manner. The synthetic protocol utilizes a low-toxicity main group metal catalyst, readily available reagents, and provides high yields of up to 96% for the synthesis of multisubstituted spirooxindole derivatives.
Review
Chemistry, Multidisciplinary
Xiao Xiao, Kaini Xu, Zhong-Hua Gao, Zhou-Hao Zhu, Changqing Ye, Baoguo Zhao, Sanzhong Luo, Song Ye, Yong-Gui Zhou, Senmiao Xu, Shou-Fei Zhu, Hongli Bao, Wei Sun, Xiaoming Wang, Kuiling Ding
Summary: Enzymes are essential for biological transformations and have attracted great attention for their structures and functions. Biomimetic chemistry has rapidly developed in response to the demand for bioactive molecules and efficient synthesis. Biomimetic asymmetric catalysis, inspired by enzymes, has been recognized as one of the most promising strategies for producing valuable chiral compounds. This review summarizes the evolution of biomimetic asymmetric catalysis in terms of biomimetic design, catalyst development, and catalytic transformations, providing insights into bridging the gap between bio-catalysis and chemical synthesis.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Organic
Zheng Liu, Sheng-Mei Lu, Bao-Qian Zhao, Hao-Dong Chen, Mu-Wang Chen, Yong-Gui Zhou
Summary: A method using zinc chloride was developed to purify compounds with pyridine structure from Mitsunobu reaction mixtures, and a sulfide anion was used to release bipyridines from Ullmann coupling reaction mixtures by competitively coordinating the copper ion. These improvements enabled the facile synthesis of the chiral 2,2'-bipyridine ligand (R-a,S,S)-C3-ACBP, achieving an overall yield of 48% at a 7 gram scale within 3-4 days without column chromatography.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Li-Xia Liu, Yu-Qing Bai, Xiang Li, Chang-Bin Yu, Yong-Gui Zhou
Summary: Combining base-promoted retro-sulfa-Michael addition with palladium-catalyzed asymmetric allenylic alkylation, a streamlined synthesis of chiral thiochromanones containing two central chiralities (including a quaternary stereogenic center) and an axial chirality (allene unit) was successfully achieved, with yields up to 98%, dr of 49.0:1, and >99% ee.
Article
Chemistry, Organic
Wen-Jun Huang, Li-Xia Liu, Yong-Gui Zhou, Bo Wu, Guo-Fang Jiang
Summary: We report a Bronsted acid-catalyzed C6 functionalization of 2,3-disubstituted indoles with 2,2-diarylacetonitriles for efficient construction of cyano-substituted all-carbon quaternary centers with excellent yields. The synthetic utility was demonstrated by the conversion of the cyano-group which enables the divergent preparation of aldehydes, primary amines and amides. Control experiments suggested that this process involves C-H oxidation of 2,2-diarylacetonitriles to in situ generate d,d-disubstituted p-quinone methide intermediates. This protocol provides an efficient method for C6 functionalization of 2,3-disubstituted indoles to construct all-carbon quaternary centers.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
