Article
Chemistry, Multidisciplinary
Tomoya Yamamoto, Tsung-Che Chang, Katsunori Tanaka
Summary: This study introduces a novel concept of a transformable protecting group that changes its properties through structural transformation. The Epoc group, developed based on this concept, can be transformed into an Fmoc-like structure with gold(iii)-catalyzed fluorene formation and removed under Fmoc-like mild basic conditions post-transformation. The Epoc group provides orthogonality to gold(iii)-labile protecting groups in solid-phase peptide synthesis and shows high turnover number of fluorene formation in aqueous media, suggesting potential applicability to biological systems.
Article
Chemistry, Multidisciplinary
Xiangwen Kong, Fang Yu, Zhizhou Chen, Fan Gong, Shuang Yang, Jinggong Liu, Benlong Luo, Xinqiang Fang
Summary: This study has successfully achieved four unprecedented and chemodivergent reactions between alpha-diketones and alkynyl alpha-diketones, leading to the construction of various biologically important molecular scaffolds. The products also exhibit promising photophysical properties and application potential, demonstrating the great value of alpha-diketones in both synthetic chemistry and material science.
SCIENCE CHINA-CHEMISTRY
(2021)
Article
Chemistry, Applied
Pierre Milcendeau, Vincent Gandon, Xavier Guinchard
Summary: Tertiary amines with a benzyl-type group undergo intramolecular addition to allenes under Au(I) catalysis. A formal 1,3-transfer of the CH2Ar group occurs during cyclization, involving two consecutive [3,3] rearrangements via a dearomatized intermediate. Protocols were developed to convert the unstable enamine products into more stable polycyclic chiral compounds in situ.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Anoop Singh, Imtiaz A. Shah, Jyothi Yadav, Preetika Sharma, Rajni Kant, Eldhose Iype, Sravendra Rana, Indresh Kumar
Summary: A simple and straightforward method for the enantioselective synthesis of indol-3-yl-piperidine has been developed, providing good yields and high enantioselectivity.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Xiangwen Kong, Fang Yu, Shengtong Niu, Fan Gong, Shuang Yang, Jinggong Liu, Benlong Luo, Xinqiang Fang
Summary: Copper-catalyzed divergent annulation reactions between alpha-diketones and alkynyl alpha-diketones have been successfully achieved, enabling the synthesis of highly functionalized and biologically important cis-hexahydro-2H-cyclopenta[b]furan and 2-hydroxydihydrofuran-3(2H)-one products. The use of earth-abundant copper catalyst, mild conditions, and shortened synthetic routes contribute to the reduction of waste production. The substituents of the nucleophilic alpha-diketones play a crucial role in determining the reaction pathways.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Physical
Srinivas Kolluru, Manvendra Singh, Bryce Gaskins, Zarko Boskovic
Summary: The study reports a nickel-catalyzed annulation reaction between o-haloarylimines and electron-poor olefins, leading to the formation of two adjacent anti stereocenters and a free secondary amine. The research characterized the key oxidative addition intermediate, identified a major path to competing products, and determined the activation energy and rate of oxidative addition complex isomerization. The sensitivity of the reaction to reaction conditions was quantitatively established, and both the scope and limitations of the method were presented.
Review
Chemistry, Multidisciplinary
Leyi Chen, Lei Wang, Quanli Shen, Yonggang Liu, Zhenghua Tang
Summary: Atomically precise metal nanoclusters have attracted significant research interest due to their quantum confinement effect and molecule-like properties. Ligand engineering, especially using alkynyl molecules, can lead to versatile interfacial bonding motifs and drastically different properties compared to thiolate ligands. This review discusses the unique advantages of alkynyl-protected metal nanoclusters, synthetic strategies, their applications in electrochemical CO2 reduction, and proposes challenges and future perspectives. The review aims to stimulate further research efforts in developing effective synthesis strategies and advancing the understanding of alkynyl-protected metal nanoclusters in catalysis.
MATERIALS CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Dan Wang, Shi-Chao Wang, Wen-Juan Hao, Shu-Jiang Tu, Bo Jiang
Summary: A new dual palladium/scandium catalysis method has been reported for the first time, allowing for the atom-economic synthesis of rotationally hindered C3-naphthylated indoles from beta-alkynyl ketones and o-alkynyl anilines in moderate to good yields and high regioselectivity. This method is tolerant to normal air conditions, uses palladium/scandium cooperative catalysts without any ligand, involves facile double annulation with various internal alkynes, and exhibits good functional group tolerance.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Guocheng Deng, Jimin Kim, Megalamane S. Bootharaju, Fang Sun, Kangjae Lee, Qing Tang, Yun Jeong Hwang, Taeghwan Hyeon
Summary: Atomically monodisperse nanostructured materials have significant importance in unraveling catalytic relationships. In this study, the synthesis and structure of a copper-containing alloy nanocluster were reported, which showed excellent catalytic activity and stability in the electrochemical CO2 reduction reaction. Density functional theory calculations revealed the mechanism behind the formation of efficient active sites.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Cheng Zhang, Qiaoying Sun, Matthias Rudolph, Frank Rominger, A. Stephen K. Hashmi
Summary: In this study, a new strategy is proposed for controlling the selectivity of catalytic reactions by adjusting the electronic and steric properties of metal complexes. The high regioselectivity of the reaction is achieved with the use of an additive, and a novel intramolecular cascade fluorination process is described for the synthesis of aryl fluorides.
Article
Chemistry, Multidisciplinary
Paul W. Davies
Summary: The combination of a nucleophilic nitrene equivalent, a triple bond, and a pi-acid catalyst has been utilized for efficient transformations to prepare azacycles. The development of an annulation strategy and the use of different N-acyl and N-heterocyclic pyridinium-N-aminides are discussed, showcasing highly efficient processes with structural and functional group tolerance. Additionally, the use of heteroatom-substituted alkynes and the reactivity of ynamides and alkynyl thioethers as enabling tools for reaction discovery are highlighted.
Article
Chemistry, Organic
Yunliang Yu, Nazarii Sabat, Meriem Daghmoum, Zhenhao Zhang, Pascal Retailleau, Gilles Frison, Angela Marinetti, Xavier Guinchard
Summary: Enantioselective tandem cycloisomerization/addition reactions of 2-alkynyl enones with 1- and 2-naphthols were investigated using gold(I) catalysts featuring hybrid phosphine-phosphoric acid chiral ligands, based on the tethered counterion-directed catalysis strategy. The reactions proceeded at low catalyst loading (0.2-1 mol%) without the need for silver additives, and the naphthols acted as both O- and C-nucleophiles, resulting in the formation of addition products with high enantioselectivity. The mechanism of these reactions was elucidated by DFT calculations.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Yan-Li Gao, Shiqing Bi, Yufei Wang, Jian Li, Ting Su, Xuchun Gao
Summary: We report the synthesis and crystal structure of a novel gold nanocluster with phosphine/alkynyl ligands, showing unique optical properties.
Article
Chemistry, Applied
Yufeng Wu, Chao Hu, Tao Wang, Lukas Eberle, A. Stephen K. Hashmi
Summary: The gold-catalyzed regioselective formation of 3-hydroxyquinoline is achieved by combining anthranils and alkynyl sulfones. The selective scission of the epoxide intermediate results from the thermodynamic stability difference of the resulting cation, as calculated by quantum chemical calculations. The subsequent semi-pinacol rearrangement leads to the 1,2-shift of an aryl or alkyl group originating from the sulfone. A gram-scale synthesis of 3-hydroxyquinoline further confirms the viability of this protocol for preparing this important scaffold.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Physical
Jessica Rodriguez, David Vesseur, Alexis Tabey, Sonia Mallet-Ladeira, Karinne Miqueu, Didier Bourissou
Summary: A (MeDalphos)AuCI complex has been discovered to efficiently catalyze the cross-coupling reaction of indoles and allyl acetates/alcohols. The reaction tolerates various functional groups and selectively produces branched C3-allylated products. It utilizes the hemilabile character of the P<^>N ligand.
Article
Chemistry, Multidisciplinary
Siyuan Su, Tongtong Wu, Yuanzhi Xia, Donald J. Wink, Daesung Lee
Summary: The cycloisomerization of alkyne-tethered N-benzoyloxycarbamates to 2-(3H)oxazolones is reported. Two catalytic systems are developed for intramolecular 5-exo-alkyne carboxyamidation and alkene isomerization. PtCl2/CO and FeCl3 are effective catalysts, but FeCl3 requires a cocatalyst for alkene isomerization. A two-step one-pot protocol is established for a broader reaction scope, involving FeCl3-catalyzed carboxyamidation and base-induced alkene isomerization. Crossover experiments suggest the involvement of acylnitrenoid intermediates in these reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Shuqi Kong, Mengyao Zhang, Shiyu Wang, Hongli Wu, Hongyan Zou, Genping Huang
Summary: Density functional theory calculations were used to study the palladium-catalyzed remote diborylative cyclization of dienes. The computations revealed a Pd(II)/Pd(IV) catalytic cycle and the involvement of a high-valent Pd(IV) species in the sigma-bond metathesis between the alkylpalladium intermediate and B(2)pin(2) via B-B oxidative addition/C-B reductive elimination. The diastereoselectivity was found to be determined by the migratory insertion into the Pd-C bond, influenced by torsional strain, steric repulsion, and C-H-O hydrogen bonding.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Yuan Gao, Zhijun Wang, Xinyu Zhang, Min Zhao, Shuai Zhang, Chao Wang, Liang Xu, Pengfei Li
Summary: In this study, novel chiral half-sandwich iridium catalysts were designed and synthesized, which enabled the preparation of a broad range of α-chiral (hetero)aryl amines with high yield and enantioselectivity. The optimized catalyst and azeotropic mixture of formic acid and triethylamine were used as the hydrogen source under mild and operationally simple conditions. This work introduced an effective chiral catalyst for the simplified synthesis of medicinally important chiral amines, and also provided a rare example of robust enantioselective transition-metal catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Jiawei Huang, Xiaoman Li, Liang Xu, Yu Wei
Summary: A three-component oxychalcogenation reaction is achieved in this study, using alkenes, diselenides/thiophenols, and H2O/alcohols as reactants. Tetrabutylammonium tribromide (TBATB) and dimethylsulfoxide (DMSO) are employed as the catalyst and terminal oxidant, respectively, enabling the difunctionalization transformation. This metal-free reaction system shows excellent functional group compatibility and provides a unified and practical approach to access beta-hydroxyl or beta-alkoxy organochalcogenides.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Peiyuan Wang, Hongli Wu, Xue-Peng Zhang, Genping Huang, Robert H. Crabtree, Xingwei Li
Summary: In this study, atroposelective access to C-N axially chiral isoquinolones was achieved via rhodium-catalyzed C-H activation of N-alkoxy benzamides and annulation with imidoyl sulfoxonium ylides. The coupling system showed excellent functional group tolerance and afforded enantiomeric products with high enantioselectivity by using different reaction conditions for a representative sulfoxonium ylide reagent. Experimental and computational studies identified a pathway involving C-H alkylation and enantio-determining formal nucleophilic substitution-C-N cyclization, mediated by the rhodium catalyst through sigma-bond metathesis as the asymmetric induction mechanism. Solvent-dependent enantiodivergence was found to originate from different levels of sigma-bond metathesis mediated by neutral versus cationic rhodium species.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemistry & Molecular Biology
Jinbo Yang, Xiangxue Cao, Lanfeng Wei, Jianshu Zhang, Jinli Zhang, Ping Liu, Liang Xu, Pengfei Li
Summary: In this study, a four-coordinated organoboron compound, aminoquinoline diarylboron (AQDAB) was used as a photocatalyst for the oxidation of silane to silanol. This method efficiently oxidizes Si-H bonds to form Si-O bonds. The corresponding silanols can be obtained in moderate to good yields at room temperature under oxygen atmospheres, providing a green protocol for the preparation of silanols.
Article
Chemistry, Organic
Changpeng Chen, Zhijun Wang, Sha Wang, Liang Xu, Xiaoming Zeng
Summary: We describe the selective cyclization of anilines with cyclobutanones and congeners using chromium catalysis. This reaction enables the formation of diastereoselective tetrahydroquinolines by linking two strained four-membered rings, leading to the synthesis of cyclobutane-fused and constrained spirotetrahydroquinolines (STHQs) and complex multiple spiro carbon-containing polyazacycles. The constrained STHQs have been utilized as versatile precursors for the synthesis of oxygen-, nitrogen-, and thio-substituted spiro analogues, as well as dioxygen-incorporated spiroazacycles.
Article
Chemistry, Organic
Huiting Wen, Yifei Chen, Lanxuan Shi, Jianhui Chen, Yanshu Luo, Yuanzhi Xia
Summary: An asymmetric hydrosilylation of alpha-oxygenated ketones was developed using Co(OAc)2 as the catalyst in combination with a chiral PAO ligand. This method provides a mild, efficient, and enantioselective access to a variety of synthetically useful 1,2-diol derivatives. The synthetic utility of this protocol was demonstrated by efficient conversion of the optically enriched products into chiral alpha-hydroxy acid, 1,3-dioxolan-2-one, ethylene oxide, and 1,2,3-1H-triazole.
Article
Chemistry, Organic
Risong Wang, Yifei Chen, Binjie Fei, Jiahao Hu, Jianhui Chen, Yanshu Luo, Yuanzhi Xia
Summary: Condition-dependent transformations between hydroximic acids and thioacetic acid were achieved, where NH4HCO3 and ethanol resulted in N-O bond cleavage to afford primary amides, and NEt3 and H2O led to O-acylation. The transformations could be scaled up to the gram level smoothly. Preliminary mechanistic studies suggested a cascade process of acylation/reduction for N-O bond cleavage.
Letter
Chemistry, Organic
Panchi Guo, Hao Jin, Jinhui Han, Liang Xu, Pengfei Li, Miao Zhan
Summary: This study demonstrates a nickel-catalyzed Negishi cross-coupling reaction for the synthesis of versatile organoboron products with high functional-group tolerance. The reaction allows for the coupling of unactivated tertiary alkyl electrophiles with boron-stabilized organozinc reagents. The importance of the Bpin group in accessing the quaternary carbon center is highlighted, and the practicality of the prepared quaternary organoboronates is showcased through their conversion to other useful compounds.
Article
Chemistry, Physical
Bing Li, Yanshu Luo, Min Liu, Yuanzhi Xia, Changkun Li
Summary: The abnormal Claisen rearrangement of phenyl allyl ether with the gamma-alkyl group is well-known, but its asymmetric version has not been reported before. In this study, a highly regio- and enantioselective allylic alkylation of 4-hydroxycoumarin was developed as a formal abnormal Claisen rearrangement. Chiral 4-hydroxycoumarins with 3-allyl groups were synthesized with high yield and enantiomeric excess using rhodium catalyst and chiral bioxazolinephosphine ligand. Experimental and theoretical investigations revealed that the stereospecific rearrangement occurs through the reversible formation of a kinetically favored cis-disubstituted spirocyclopropane intermediate.
Article
Multidisciplinary Sciences
Yishou Wang, Xiaohan Zhu, Deng Pan, Jierui Jing, Fen Wang, Ruijie Mi, Genping Huang, Xingwei Li
Summary: Here, the authors report the construction of diverse classes of diaxially chiral biaryls containing N-N and C-N/C-C diaxes in excellent stereo- and diastereoselectivity. The N-N chiral axis in the products allows for solvent-driven diastereodivergence, as demonstrated in the coupling of benzamides and sterically hindered alkynes. The mechanism of diastereodivergence is elucidated through computational studies, revealing the role of hexafluoroisopropanol (HFIP) as a solvent and ligand.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Xinyi Song, Hongli Wu, Jinjin Yang, Wentao Zhao, Genping Huang
Summary: Density functional theory calculations were used to investigate the mechanism of copper-catalyzed borocarbonylation of imines with B(2)pin(2) and alkyl iodides. The calculations showed that the reaction starts with the selective migratory insertion of the C-N double bond into the Cu-B bond to form the key alpha-boryl amido-copper complex, which can undergo a stepwise rearrangement to give alpha-amino alkyl-copper species. The C-I bond cleavage of alkyl iodide through halogen-atom abstraction, radical association, and reductive elimination leads to the formation of alpha-boryl amide and alpha-amino ketone products. The regioselectivity of the reaction is determined by the competition between the 1,2-rearrangement and C-I bond cleavage from the alpha-boryl amido-copper complex, which is in good agreement with experimental observations.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Jiawei Huang, Xiaoman Li, Yu Wei, Zhigang Lei, Liang Xu
Summary: A novel photoredox process using AQDAB and TBAI as co-catalysts has been developed for N-functionalization of NH-sulfoximines/sulfonimidamides. The protocol offers good to excellent yields of N-sulfenylated and N-phosphonylated products without the need for metallic (photo)catalysts, external oxidants, or acidic/basic additives. This method is tolerant to a wide range of functional groups and allows the N-phosphonylation of NH-sulfonimidamides for the first time.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Lanfeng Wei, Wenbo Bai, Zhiyan Hu, Zhiyong Yang, Liang Xu
Summary: The study developed a unified metal-free photooxidative platform for the cleavage of C-heteroatom bonds, using AQDAB complex as the photocatalyst to induce the oxidation process. This method allows for chemoselective cleavage of C-N, C-S, and C-Se bonds, broadening the potential applications of oxidation in synthetic chemistry. It established a photooxidation system for formal carbonylation of C-heteroatom (N, S, Se) bonds.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Faiza Diaba, Gisela Trenchs
Summary: The first violet light-mediated synthesis of gamma- and delta-lactams from N-alkenyl trichloroacetamides is reported in this paper. The reactions are conducted in tetrahydrofuran or 2-methyltetrahydrofuran as the sole solvent without catalysts or additives, under non-anhydrous conditions in an air atmosphere where the solvent serves as the radical initiator.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Feroze Hussain, Sajjad Ahmed, Ashiq Hussain Padder, Qazi Naveed Ahmed
Summary: This study reports a novel and efficient one-pot synthesis method for mixed phosphorotrithioates, which does not require supplementary additives and shows broad applicability.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Hyunjin Oh, Ikyon Kim
Summary: A new 1,2,4-triazole-pyrrolo[1,2-a]pyrazine hybrid system, 6-acylpyrrolo[1,2-a][1,2,4]triazolo[5,1-c]pyrazine, was synthesized using a catalyst-free method. This method involved sequential exposure of pyrrole-2-carbonitrile-derived substrates to DMF-DMA and acyl hydrazide, resulting in the formation of acylated pyrazine and 1,2,4-triazole rings, enabling the installation of various substituents at specific positions on the core skeleton.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Ming Yan, Si-fan Wang, Yong-po Zhang, Jin-zhong Zhao, Zhuo Tang, Guang-xun Li
Summary: Here we developed an efficient photocatalytic approach for the convenient preparation of sulfinamides. The reaction allows for the gram-scale preparation of sulfinamides and the one-pot synthesis of various sulfonyl amides.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Farzaneh Bandehali-Naeini, Zahra Tanbakouchian, Noushin Farajinia-Lehi, Nicolas Mayer, Morteza Shiri, Martin Breugst
Summary: Two tandem catalytic systems were developed for the synthesis of novel 3,4-disubstituted maleimides using the same Ugi adducts. Different maleimide structures can be synthesized using either Pd or Cu catalysis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Tanya Raghava, Anjan Chattopadhyay, Subhadeep Banerjee, Nivedita Sarkar
Summary: Amine substitution of two ortho fluorine atoms of tetrafluoroterephthalonitrile through SNAr chemistry is easily achievable. But further fluorine substitution is only possible under forcing conditions, yielding valuable fluorophores for bioimaging.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Review
Chemistry, Organic
Anju Chadha, Santosh Kumar Padhi, Selvaraj Stella, Sowmyalakshmi Venkataraman, Thangavelu Saravanan
Summary: Alcohol dehydrogenases are enzymes that use cofactors for oxidation or reduction reactions of alcohols or carbonyl compounds. They are utilized in green chemistry and have applications in the production of pharmaceuticals. Recombinant enzymes have solved the challenge of producing purified enzymes in large quantities. Engineered alcohol dehydrogenases have been used in asymmetric synthesis in industry. Various methods have been established for regenerating expensive cofactors to make the enzymatic process more efficient and economically viable.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
