Article
Multidisciplinary Sciences
Yuya Ashida, Yuto Onozuka, Kazuya Arashiba, Asuka Konomi, Hiromasa Tanaka, Shogo Kuriyama, Yasuomi Yamazaki, Kazunari Yoshizawa, Yoshiaki Nishibayashi
Summary: The development of a nitrogen fixation process that relies on renewable energy, such as visible light, is a goal in sustainable chemistry. In this study, the authors establish an iridium and molybdenum-catalysed process for synthesizing ammonia from dinitrogen under ambient reaction conditions and visible light irradiation.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Dongari Yadagiri, Pazhamalai Anbarasan
Summary: This article discusses the synthesis of heterocyclic compounds starting from N-sulfonyl-1,2,3-triazoles and alpha-diazocarbonyl compounds using transition metal catalysts. Functionalization of alpha-imino(carbonyl) metal carbenes has been achieved through in-situ generated metal-stabilized ylides, leading to the efficient synthesis of various synthetically important intermediates and heterocyclic compounds.
Article
Multidisciplinary Sciences
Kai Wang, Zi-Hao Deng, Si-Jun Xie, Dan-Dan Zhai, Hua-Yi Fang, Zhang-Jie Shi
Summary: Ammonia and nitric acid are key platform chemicals to introduce nitrogen into organic molecules in chemical industry, however gaseous N-2 would be a more direct and available source of nitrogen. Here, the authors report a direct catalytic nitrogenation to afford valuable arylamines and N-heterocycles from organohalides using dinitrogen (N-2) as the nitrogen source.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
David N. Stephens, Robert K. Szilagyi, Paige N. Roehling, Navamoney Arulsamy, Michael T. Mock
Summary: We have reported a nickel complex that can catalyze the oxidation of ammonia to dinitrogen under ambient conditions. By using aryloxyl or N-oxyl radicals as H atom acceptors, the N-H bonds of coordinated NH3 ligands can be cleaved to generate N-2 molecules. Isotopic nitrogen studies have identified a bridging Ni-hydrazine product, supported by computational models, indicating a bimetallic homocoupling mechanism for N-N bond formation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Christian M. Johansen, Emily A. Boyd, Jonas C. Peters
Summary: Inspired by reductive photoredox catalysis, photodriven transfer hydrogenation reactions are attractive for deep reductions of small molecules. In this study, a synthetic photo-catalyst system was developed, enabling the catalytic reduction of nitrogen to ammonia. The reduction of other substrates was also investigated.
Article
Multidisciplinary Sciences
Yasuhiro Ohki, Kenichiro Munakata, Yuto Matsuoka, Ryota Hara, Mami Kachi, Keisuke Uchida, Mizuki Tada, Roger E. Cramer, W. M. C. Sameera, Tsutomu Takayama, Yoichi Sakai, Shogo Kuriyama, Yoshiaki Nishibayashi, Kazuki Tanifuji
Summary: Researchers have successfully synthesized a metal-sulfur cluster and demonstrated its ability to reduce N-2. This discovery helps to understand the mechanism of nitrogen fixation in nature and provides new insights for the production of nitrogen fertilizers.
Article
Chemistry, Multidisciplinary
Marios Kidonakis, Manolis Stratakis
Summary: Supported Au nanoparticles on TiO2 are capable of catalyzing the reduction of alpha-diazocarbonyl compounds into a methylene group in methanol using NH3BH3 or NaBH4. The reaction occurs rapidly at room temperature and differs from the reaction catalyzed by Pt/CeO2, which leads to hydrazones instead. Under stoichiometric Au-catalyzed conditions, ketone-type carbonyls remain intact, in contrast to the uncatalyzed conditions where they are selectively reduced by the boron hydride reagent.
Article
Chemistry, Physical
Junxian Gao, Lingling Tang, Zhizhang Shen, Yuming Dong, Zhenyu Wang, Jinze Lyu, Ji Li, Hanqing Yu
Summary: Combining LaFeO3 and PdOx can enhance the catalytic ozonation of toluene by simultaneously converting the energy from ultraviolet, visible, and infrared light. Additionally, PdOx loading significantly promotes the separation efficiency of photogenerated charge carriers and expands the valid spectrum of photoelectric effect from ultraviolet to visible regions.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2021)
Review
Biochemistry & Molecular Biology
Luiz Oliveira, Marcio Pereira, Ana Pacheli Heitman, Jose Filho, Cinthia Oliveira, Maria Ziolek
Summary: This article discusses the need to develop new technologies that can utilize renewable resources due to the consumption and demand for products based on fossil fuels. The use of biomass to obtain chemical intermediates and fuels has emerged as an important area of research in recent years. It is a renewable source of carbon and does not contribute to additional greenhouse gas emissions due to the absorption of CO2 through photosynthesis.
Article
Chemistry, Physical
Bingxue Wang, Shan Huang, Lisheng Yang, Qiang Fu, Yuxiang Bu
Summary: This study investigates various external means to regulate the catalytic properties of Fe-2 on g-C3N4 for the electrochemical reduction of nitrogen to ammonia. The results show that applying tensile stress to the substrate or doping with electropositive Na atoms can effectively reduce the overpotential of the reaction through different mechanisms, potentially improving reaction selectivity. This work sheds new light on designing and improving electrocatalysts for the nitrogen reduction reaction.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Article
Chemistry, Multidisciplinary
Hao Luo, Eric P. Weeda, Manar Alherech, Colin W. Anson, Steven D. Karlen, Yanbin Cui, Cliff E. Foster, Shannon S. Stahl
Summary: Biomass pretreatment methods can lead to modification, degradation, or low yields of lignin, but catalytic fractionation approaches can effectively separate polymeric sugar and lignin fractions with the help of a catalyst, producing oxygenated aromatics suitable for polymer synthesis and biological funneling to value-added products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Xiaohui Zhang, Tianyi Wang, Congyun Zhang, Yihui Zou, Jun Ren, Pengcheng Cai, Chenghua Sun, Dongjiang Yang
Summary: This study systematically investigates the nitrogen reduction reaction (NRR) performance of Fe-1/2/3 clusters anchored on N-doped graphene. The results demonstrate that Fe-2 cluster supported by two N atom-modified single-vacancy graphene exhibits superior catalytic performance with the lowest energy barrier and efficient selectivity among the candidates.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Anna Fajdek-Bieda, Andrzej Perec, Aleksandra Radomska-Zalas
Summary: This paper utilizes response surface methodology to model the transformation process of geraniol, studying the relationships between multiple explanatory variables and one or more response variables using statistical and mathematical modeling methods. Interactions between process variables are examined using statistical techniques. The influence of key process parameters, including temperature, catalyst concentration, and reaction time, on conversion and selectivity is presented in the form of second-order polynomials. The aim is to identify optimal process conditions that yield high values of the process function.
Article
Chemistry, Organic
Jiyoung Kim, Eun Jeong Yoo
Summary: By carefully controlling the reaction kinetics and utilizing a silver catalyst, a catalytic ring expansion of activated heteroarenes was achieved through 1,4-dearomative addition to construct fused azepines. The developed methodology offers an innovative approach for the synthesis of biologically relevant multifused azepines, showcasing excellent substrate scope and selectivity.
Article
Chemistry, Physical
Junxian Gao, Lingling Tang, Zhizhang Shen, Yuming Dong, Zhenyu Wang, Jinze Lyu, Ji Li, Han-Qing Yu
Summary: The coupling of solar energy conversion and catalytic ozonation using a non-noble-metal SiC/CeO2 system was found to effectively eliminate toluene. SiC enhanced the conversion of visible and infrared light to heat, increasing the reaction temperature. SiC also transferred electrons to CeO2, generating more active sites and promoting the reaction efficiency. 25%SiC-CeO2 exhibited outstanding performance in toluene mineralization.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2022)
Article
Chemistry, Multidisciplinary
Yingxiang Ye, Shikai Xian, Hui Cui, Kui Tan, Lingshan Gong, Bin Liang, Tony Pham, Haardik Pandey, Rajamani Krishna, Pui Ching Lan, Katherine A. Forrest, Brian Space, Timo Thonhauser, Jing Li, Shengqian Ma
Summary: This study introduces a novel strategy to promote the separation of C2H2/CO2 mixtures by regulating a hydrogen-bonding nanotrap on the pore surface of three isostructural metal-organic frameworks. Among them, MIL-160 demonstrates an ultrahigh C2H2 storage capacity and superior C2H2/CO2 selectivity due to its multiple hydrogen-bonding interaction with C2H2.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Chemistry, Organic
Yong-Liang Su, Michael P. Doyle
Summary: α-Aminoalkyl radicals are easily synthesized and used as reaction activators to transform organic halides or sulfonium salts into highly reactive radical species. This review summarizes the emerging chemistry in the field, providing new pathways for transformations of halides and sulfonium salts.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Physical
Yong-Liang Su, Geng-Xin Liu, Luca De Angelis, Ru He, Ammar Al-Sayyed, Kirk S. Schanze, Wen-Hao Hu, Huang Qiu, Michael P. Doyle
Summary: This study demonstrates the efficient generation of functionalized derivatives through photocatalyzed multicomponent reactions using nitrogen aromatic heterocycles, alkenes, and diazo compounds. The reaction shows high functional group tolerance and exacting regioselectivities. Mechanistic studies, including photophysical measurements, provide insights into this radical cascade reaction.
Article
Biochemistry & Molecular Biology
Chaochao Yan, Peilin Zhao, Chan Lu, Yang Yu, Junzhou Huang
Summary: The main goal of retrosynthesis is to break down desired molecules into available building blocks. Existing template-based methods are limited by a fixed template selection pattern and lack the ability to discover new reactions. To overcome this limitation, we propose an innovative retrosynthesis prediction framework that can generate new templates beyond the training templates. We also introduce an effective reactant candidate scoring model that captures atom-level transformations and outperforms previous methods. Experimental results demonstrate the ability of our method to generate novel templates for reactions not covered by training templates.
Article
Chemistry, Multidisciplinary
Ming Bao, Xiongda Xie, Jingjing Huang, Michael P. Doyle, Zhi Ren, Haibo Yue, Xinfang Xu
Summary: In this study, an Ag/Au-catalyzed cascade reaction of alkyne embedded diazoketones with indoles has been reported. Mechanistic studies indicate that the reaction involves a [4+2] cycloaddition followed by a retro-Michael addition/carbene N-H insertion process with gold catalysis, and a dearomatization/rearomatization sequence with silver catalysis, leading to the selective construction of N-doped polycyclic aromatic hydrocarbons (PAHs) with diverse structures and functional groups.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Ming Bao, Karlos Lopez, Raj Gurung, Hadi Arman, Michael P. Doyle
Summary: A highly enantioselective synthesis of chiral dihydro-3H-carbazole-2-carboxylate derivatives is achieved via a one-pot cascade reaction catalyzed by nickel(II) perchlorate hexahydrate and scandium(III) trifluoromethanesulfonate. The reaction proceeds under mild conditions and provides the desired products in high yields and enantioretention. Furthermore, these dihydro-3H-carbazole-2-carboxylates can be transformed into decarboxylated compounds through hydrolysis and decarboxylation under unexpectedly mild reaction conditions, giving moderate yields with high retention of enantiomeric purity.
Article
Chemistry, Multidisciplinary
Luca De Angelis, Graham C. Haug, Gildardo Rivera, Soumen Biswas, Ammar Al-Sayyed, Hadi Arman, Oleg Larionov, Michael P. Doyle
Summary: One important reaction of 1,2,3-triazines is the inverse electron demand Diels-Alder (IEDDA) cycloaddition with a dienophile, which proceeds through nucleophilic addition to the triazine followed by N-2 loss and cyclization. Previous studies have not provided a comprehensive understanding of the site of nucleophilic addition on the triazine. This study investigated the C-, N-, H-, O-, and S-nucleophilic additions on 1,2,3-triazine and 1,2,3-triazine-1-oxide frameworks and revealed the differentiation of addition at the 4- and 6-positions. Computational studies further examined the factors influencing the outcomes of these reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Soumen Biswas, Luca De Angelis, Gildardo Rivera, Hadi Arman, Michael P. Doyle
Summary: 1,2,3-Triazine 1-oxides are highly effective substrates for inverse electron demand Diels-Alder reactions. These stable heterocyclic compounds, formed from vinyldiazoacetates via reaction with tert-butyl nitrite, undergo clean nucleophilic addition reactions with amidines to form pyrimidines, with beta-ketocarbonyl compounds and related nitrile derivatives to form polysubstituted pyridines, and with 3/5-aminopyrazoles to form pyrazolo[1,5-a]pyrimidines, in high yields. These reactions, catalyzed by bases, are rapid at room temperature and allow for a range of structural modifications.
Article
Chemistry, Organic
Michael P. Doyle, Ming Bao
Summary: This study achieved a highly enantioselective synthesis of substituted pyrrolidines and 1,2-oxazinanes via stereoretentive [3 + 2]/[3 + 3]-cycloaddition of nonracemic donor-acceptor cyclopropanes with imines, triazines, and nitrones. The reactions were conducted under mild conditions and showed good to high yields with broad applicability. Compared to previous approaches using racemic cyclopropane reactants and chiral ligand catalysts, this study utilized enantioenriched donor-acceptor cyclopropanes as reactants with achiral catalysts.
Article
Chemistry, Medicinal
Yang Yu, Junhong Huang, Hu He, Jing Han, Geyan Ye, Tingyang Xu, Xianqiang Sun, Xiumei Chen, Xiaoming Ren, Chunlai Li, Huijuan Li, Wei Huang, Yangyang Liu, Xinjuan Wang, Yongzhi Gao, Nianhe Cheng, Na Guo, Xibo Chen, Jianxia Feng, Yuxia Hua, Chong Liu, Guoyun Zhu, Zhi Xie, Lili Yao, Wenge Zhong, Xinde Chen, Wei Liu, Hailong Li
Summary: Selective CDK2 inhibitors have the potential to effectively treat CDK2-dependent cancers and overcome drug resistance. The discovery of QR-6401 (23), a highly potent and selective macrocyclic CDK2 inhibitor, was accelerated by the application of generative models and structure-based drug design. QR-6401 (23) demonstrated robust antitumor efficacy in an OVCAR3 ovarian cancer xenograft model via oral administration.
ACS MEDICINAL CHEMISTRY LETTERS
(2023)
Article
Multidisciplinary Sciences
Luca De Angelis, Chao Pei, Ana L. Narro, Daniel Wherritt, Rene M. Koenigs, Michael P. Doyle
Summary: The synthesis and characterization of organic compounds with unique atom or functional group connectivity is a significant interest for chemists. Polycarbonyl compounds, in which multiple carbonyl groups are directly adjacent and influence each other's reactivity, have been extensively studied. However, little is known about 1,2,3,4-tetracarbonyl compounds. In this study, a synthesis strategy involving C-nitrosation of enoldiazoacetates is reported, which allows for the synthesis of 1,2,3,4-tetracarbonyl compounds where each carbonyl group is orthogonally masked.
NATURE COMMUNICATIONS
(2023)
Review
Chemistry, Physical
Ming Bao, Michael P. Doyle
Summary: The [3+n]-cycloaddition reactions using chiral catalysts and racemic cyclopropanes or achiral catalysts and chiral, non-racemic cyclopropanes have proven to be important transformations for the synthesis of carbocyclic and heterocyclic compounds, showing both mechanistic and structural advantages in ring formation.
Article
Chemistry, Medicinal
Yang Yu, Junhong Huang, Hu He, Jing Han, Geyan Ye, Tingyang Xu, Xianqiang Sun, Xiumei Chen, Xiaoming Ren, Chunlai Li, Huijuan Li, Wei Huang, Yangyang Liu, Xinjuan Wang, Yongzhi Gao, Nianhe Cheng, Na Guo, Xibo Chen, Jianxia Feng, Yuxia Hua, Chong Liu, Guoyun Zhu, Zhi Xie, Lili Yao, Wenge Zhong, Xinde Chen, Wei Liu, Hailong Li
Summary: Selective CDK2 inhibitors have the potential to be effective therapeutics for CDK2-dependent cancers, and can overcome drug resistance caused by high CCNE1 expression or CCNE1 amplification induced by CDK4/6 inhibitors. The integration of generative models and structure-based drug design (SBDD) in early drug discovery has led to the discovery of a highly potent and selective macrocyclic CDK2 inhibitor QR-6401 specialIntscript. QR-6401 specialIntscript demonstrated robust antitumor efficacy in an OVCAR3 ovarian cancer xenograft model via oral administration.
ACS MEDICINAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Ming Bao, Karlos Lopez, Raj Gurung, Hadi Arman, Michael P. Doyle
Summary: A highly enantioselective synthesis of chiral dihydro-3H-carbazole-2-carboxylate derivatives is achieved via a one-pot cyclopentannulation-rearrangement cascade reaction. The reaction is catalyzed by nickel(II) perchlorate hexahydrate and scandium(III) trifluoromethanesulfonate, and involves the use of 3-methylindole and non-racemic donor-acceptor cyclopropanes. The resulting products show high yields and enantioretention under mild reaction conditions, and further transformation into decarboxylated compounds can be achieved with moderate yields and high enantiomeric purity.
Article
Chemistry, Physical
Yi Xie, Yanshu Shi, Hui Cui, Rui-Biao Lin, Banglin Chen
Summary: The newly developed ultramicroporous material nickel nitroprusside (Ni-NP) demonstrates high efficiency in separating propylene from propane at ambient conditions, with high selectivity and absorption capacity for C3H6/C3H8 separation. The material can be easily obtained through a simple precipitation reaction under ambient conditions, highlighting its potential for scale-up production.
