Article
Chemistry, Applied
Lilian Geniller, Marc Taillefer, Florian Jaroschik, Alexis Prieto
Summary: The Ni-photoredox catalyzed desulfurative cross-coupling reaction enables the synthesis of various unsymmetrical diarylmethane molecules under mild reaction conditions, providing new transformations of abundant, naturally occurring thiols.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Qi Zhu, En Zhao, Yajing Shen, Zupeng Chen, Weiwei Fang
Summary: An easy to prepare nickel-coordinated mesoporous graphitic carbon nitride (Ni-mpg-CN) was used as a heterogeneous photocatalyst to efficiently catalyze the photocatalytic C-N cross-coupling of (hetero)aryl bromides and aliphatic amines, yielding the desired monoaminated products in good yields. Furthermore, the synthesis of the pharmaceutical tetracaine was successfully achieved, highlighting its practical applicability.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Physical
Michael D. Zott, Virginia M. Canestraight, Jonas C. Peters
Summary: This study provides a detailed insight into the photochemistry of a highly reducing, highly luminescent dicopper system, demonstrating its mechanism in the single-electron reduction reaction of benzyl chlorides. The [Cu-2]* excited state serves as the outer-sphere photoreductant for benzyl chloride substrates, while the oxidized byproduct [Cu-2](+) is electrochemically recycled, showcasing a catalytic electrophotochemical C-C coupling process.
Article
Chemistry, Multidisciplinary
Yangzhong Qin, Rui Sun, Nikolas P. Gianoulis, Daniel G. Nocera
Summary: The researchers conducted a comprehensive mechanistic study of photoredox nickel-catalyzed C-S cross-coupling, revealing a self-sustained productive Ni(I/III) cycle, the role of in situ formed pyridinium iodide as a dominant quencher, and critical intermediates in the reaction pathway. These mechanistic insights not only provided a complete reaction cycle but also allowed for optimization of reaction efficiency and broadening the substrate scope.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Qi Yukki Li, Samuel N. Gockel, Grace A. Lutovsky, Kimberly S. DeGlopper, Neil J. Baldwin, Mark W. Bundesmann, Joseph W. Tucker, Scott W. Bagley, Tehshik P. Yoon
Summary: Reactions that allow for the formation of carbon-nitrogen, carbon-oxygen, and carbon-carbon bonds are crucial in synthetic chemistry. This study presents a copper-mediated, net-oxidative decarboxylative coupling reaction under visible-light irradiation, which enables the conversion of substrates without requiring harsh reaction conditions.
Review
Chemistry, Multidisciplinary
Fu-Dong Lu, Jun Chen, Xuan Jiang, Jia-Rong Chen, Liang-Qiu Lu, Wen-Jing Xiao
Summary: Asymmetric transition metal catalysis with light intervention offers a practical alternative strategy for constructing complex organic molecules with excellent regio- and enantioselectivities. The recent advances in this field, including a concise analysis of substrate scope and mechanistic scenarios governing stereocontrol, provide a comprehensive understanding of the synthetic utility and potential of this methodology.
CHEMICAL SOCIETY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Yunhui Feng, Hang Luo, Fangnian Yu, Qian Liao, Luqing Lin
Summary: Here, we present a visible-light-promoted single nickel catalysis for achieving various C-N couplings of aryl chlorides/bromides and diverse N-nucleophiles using sodium iodide as the activator. The single nickel catalyst plays a dual role in halogen exchange and C-N coupling, which are crucial for obtaining the desired coupling products. This catalytic process eliminates the need for an exogenous photocatalyst and offers a sustainable and efficient approach for mild C-N coupling. Experimental studies, along with UV-vis and NMR analyses, demonstrate that the halogen exchange between both Ni-II and Ni-III-halide complexes and the iodide anion is a significant process in the formation of coupling products.
Article
Chemistry, Organic
Ethan M. Decicco, Simon Berritt, Thomas Knauber, Steven B. Coffey, Jie Hou, Matthew S. Dowling
Summary: Conditions suitable for the decarboxylative cross-electrophile coupling of NHP esters and a wide range of (hetero)-aryl bromides were developed. The use of ligand L3 and iodide salts, as well as excess zinc, significantly improved the reaction yield.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Ethan M. Decicco, Simon Berritt, Thomas Knauber, Steven B. Coffey, Jie Hou, Matthew S. Dowling
Summary: This study reports the development of suitable conditions for the decarboxylative cross-electrophile coupling of redox-active NHP esters and a wide range of (hetero)aryl bromides. The use of ligand L3, iodide salts, and excess heterogeneous zinc significantly improved the yield of the reaction, enabling the successful utilization of aryl bromides. Various NHP esters and aromatic/heteroaromatic bromides relevant to medicinal chemistry showed good reactivity under the optimized conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Zhilong Li, Leitao Huan, Jian Li, Xiaomin Shu, De Zhong, Wenjing Zhang, Haohua Huo
Summary: In this study, an unprecedented enantioselective cross-electrophile coupling (XEC) of α-amino acid derivatives with aryl bromides was achieved using alcohols as reducing agents via Ni/photoredox catalysis. The method utilizes photocatalytically generated α-hydroxyalkyl radicals to convert alkyl electrophiles to alkyl radicals that can selectively couple with aryl bromides. The scalable protocol allows modular access to valuable enantioenriched benzylic amines and can be applied to late-stage diversification with broad functional group tolerance. Mechanistic studies support the versatility of this alcohol-based reactivity for radical generation and subsequent asymmetric cross-coupling. We expect that this alcohol-based cross-coupling will serve as a general platform for the development of appealing yet challenging enantioselective XECs.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Liangliang Song, Lingchao Cai, Lei Gong, Erik V. Van der Eycken
Summary: Copper-catalyzed enantioselective coupling reactions have been extensively studied for the rapid synthesis of chiral molecules. Despite progress in polar and radical mechanisms, the development of general and practical strategies for the regio-, enantio-, and diastereoselective assembly of stereogenic centers remains challenging. The integration of photocatalysis with asymmetric copper catalysis offers new reaction pathways and diverse chiral compounds, expanding the scope of radical chemistry. This review provides a summary of recent advances in photoinduced copper-catalyzed enantioselective coupling reactions, with a discussion on the mechanistic aspects.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Cheng Chen, Minyan Wang, Hongjian Lu, Binlin Zhao, Zhuangzhi Shi
Summary: Alkyl thianthrenium salts have been synthesized as reliable alkylation reagents, which can readily engage in copper-catalyzed Sonogashira and Kumada reactions to build C(sp(3))-C(sp) bonds under mild photochemical conditions. The method demonstrates great functional breadth and compatibility, even with sensitive Cl, Br, and I atoms.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Hui Wang, Wangyujing Han, Adam Noble, Varinder K. Aggarwal
Summary: This study reports a nickel/photoredox-catalyzed site-selective mono-deboronative arylation of 1,2-bis-boronic esters, which allows for selective coupling of the more sterically hindered secondary/tertiary positions. This is achieved by utilizing a 1,2-boron shift of primary β-boryl radicals to the thermodynamically favored secondary/tertiary radicals for arylation. The mild conditions of this method are suitable for a wide range of aryl halides, resulting in good yields and high regioselectivity. Additionally, this method allows for stereodivergent coupling of cyclic cis-1,2-bis-boronic esters to give trans-substituted products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Xiao Dan, Qian Yang, Liuzhuang Xing, Yurong Tang, Wentao Wang, Yunfei Cai
Summary: A fully heterogeneous metallaphotocatalytic C-C cross-coupling of aryl/vinyl halides with alkyl/allyl trifluoroborates has been developed using an integrated bipyridyl-Ni-(II)-carbon nitride as a stable and recyclable bifunctional catalyst. This visible-light-mediated heterogeneous protocol enables the sustainable synthesis of diverse valuable diarylmethanes and allylarenes in high efficiency.
Article
Chemistry, Multidisciplinary
Chao Jiang, Pinhong Chen, Guosheng Liu
Summary: In this study, a novel reaction technique combining photocatalysis and copper catalysis was developed for the radical decarboxylative C(sp(3))-C(sp(3)) cross-coupling of NHPI esters and cyclopropanols, leading to the efficient synthesis of ss-benzyl ketones. The terpyridin-4'-one ligand played a vital role in the reaction by facilitating the capture of benzylic radicals by alkyl-copper species generated through the copper-catalyzed ring-opening of cyclopropanols. The reaction exhibited broad substrate scope and wide functional group compatibility, providing a new approach for C(sp3)-C(sp3) bond formation.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Ze-Peng Yang, Dylan J. Freas, Gregory C. Fu
Summary: Chiral dialkyl carbinamines are important compounds in various fields, and two mild methods for their catalytic enantioconvergent synthesis using a chiral nickel catalyst have been reported. These methods are versatile and can be used for the synthesis of a variety of functionalized dialkyl carbinamines, including a one-pot variant for generating enantioenriched compounds from commercially available amino acid derivatives. The utility of these methods has been demonstrated in the efficient catalytic enantioselective synthesis of a range of target molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Ze-Peng Yang, Dylan J. Freas, Gregory C. Fu
Summary: Interest in unnatural alpha-amino acids has grown rapidly in recent years, and developing efficient methods for their enantioselective synthesis is a key objective. The use of a nickel-based chiral catalyst has enabled the enantioconvergent coupling of racemic alkyl electrophiles with alkylzinc reagents, yielding protected unnatural alpha-amino acids. This novel cross-coupling method has successfully produced enantioenriched unnatural alpha-amino acids for the synthesis of bioactive compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Ji-Kang Jin, Kun Wu, Xin-Yi Liu, Guo-Quan Huang, Yong-Liang Huang, Dong Luo, Mo Xie, Yifang Zhao, Weigang Lu, Xiao-Ping Zhou, Jian He, Dan Li
Summary: Charge separation is crucial in regulating photochemical properties in photocatalysts design. Metal-organic frameworks (MOFs) are promising candidates for heterogeneous photocatalysis due to their designability and photon absorption tunability. A pyrazole-benzothiadiazole-pyrazole organic molecule with a donor-acceptor-donor conjugated pi-system was designed for fast charge separation, resulting in a more effective heterogeneous photocatalyst JNU-204, which demonstrated stability and reusability in aerobic oxidation reactions under visible-light irradiation. JNU-204 also showed applications in the synthesis of marine natural product core skeletons.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Heejun Lee, Jun Myun Ahn, Paul H. Oyala, Cooper Citek, Haolin Yin, Gregory C. Fu, Jonas C. Peters
Summary: Photoinduced, copper-catalyzed couplings of nitrogen nucleophiles with alkyl electrophiles have been shown to be an attractive approach for achieving enantioselective C-N bond formations. This study provides mechanistic insight into a previously reported photoinduced, copper-catalyzed enantioconvergent C-N coupling. Experimental and computational results support the proposed intermediates and their chemical stability and competence in producing the desired C-N coupling product with enantioselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Hyungdo Cho, Hidehiro Suematsu, Paul H. Oyala, Jonas C. Peters, Gregory C. Fu
Summary: Transition-metal catalysis of substitution reactions of alkyl electrophiles by nitrogen nucleophiles is an important strategy for synthesizing higher-order amines and controlling their stereochemistry. This study reports the photo-induced enantioconvergent coupling of racemic tertiary alkyl electrophiles with aniline nucleophiles using a readily accessible chiral copper catalyst. The mechanism of this catalytic process has been elucidated using various tools, leading to the identification of key copper-based intermediates in the proposed cycle.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Inorganic & Nuclear
Xia Wu, Xiao Xiong, Jia-Li Li, Dong Luo, Kun Wu, Yu-Bai Wei, Xin-Yi Liu, Weigang Lu, Dan Li, Jian He
Summary: Due to misuse and poor management, antibiotics pose a significant threat to the ecological environment and human health. Developing highly sensitive and effective sensors to detect environmental contaminants is a crucial and challenging task. Biological metal-organic frameworks, as a new class of desirable biocompatible materials, show promise as a viable platform for sensing applications.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Ben Ma, Qi Xia, Deyang Wang, Ji-Kang Jin, Zekun Li, Qiu-Jiang Liang, Meng-Ying Sun, Dongyi Liu, Li-Juan Liu, Hui-Xing Shu, Jun Yang, Dan Li, Jian He
Summary: Visible-light copper photocatalysis has become a viable technology for sustainable synthetic processes. In this study, a metal-organic framework (MOF)-supported copper(I) photocatalyst was developed for iminyl radical-mediated reactions. The heterogenized copper photosensitizer exhibited higher catalytic activity than its homogeneous counterpart due to site isolation. The immobilization of copper species on MOF supports using a hydroxamic acid linker allowed for high recyclability of the heterogeneous catalysts and the preparation of previously unavailable monomeric copper species through post-synthetic modification on MOF surfaces. This study highlights the potential of MOF-based heterogeneous catalytic systems in addressing challenges in synthetic methodologies and mechanistic investigations of transition-metal photoredox catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Shengli Zhuang, Dong Chen, Wai-Pan Ng, Li-Juan Liu, Meng-Ying Sun, Dongyi Liu, Tehseen Nawaz, Qi Xia, Xia Wu, Yong-Liang Huang, Seungkyu Lee, Jun Yang, Jun Yang, Jian He
Summary: By substituting neutral phosphine ligands for surface anionic thiolate ligands, two atomically precise defective Au-44 nanoclusters were successfully formed. The Au-44(PPh3)(TBBT)(26) nanocluster with major structural defects showed superior electrocatalytic performance in the CO2 reduction to CO, which was attributed to the active site near the defects.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Caiyou Chen, Gregory C. C. Fu
Summary: Carbon-oxygen bonds are common in organic molecules, making methods for their construction with control of stereoselectivity important. The widely used Williamson ether synthesis has limitations in terms of scope and stereochemistry due to its reaction mechanism. Transition-metal catalysis has the potential to overcome these limitations but progress has been limited, especially in controlling enantioselectivity. We demonstrate that a readily available copper catalyst can achieve enantioconvergent substitution reactions of α-haloamides with oxygen nucleophiles, offering a promising solution to the challenge of enantioselective alkylations of heteroatom nucleophiles.
Article
Multidisciplinary Sciences
Li-Juan Liu, Fahri Alkan, Shengli Zhuang, Dongyi Liu, Tehseen Nawaz, Jun Guo, Xiaozhou Luo, Jian He
Summary: This study reports a new type of gold nanoclusters, whose intrinsic chirality arises solely from the arrangement of the organic components on their surface. The highly dynamic behaviors of aromatic rings in the thiolates assembled via pi - pi stacking and C - H center dot center dot center dot pi interactions explain the non-asymmetrically induced inner structures of these nanoclusters. This work introduces an important class of nanoclusters with intrinsic chirality from surface layers and helps elucidate the transition of gold nanoclusters from their molecular to metallic states.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Xiaoyu Tong, Ze-Peng Yang, Carlos E. Del Angel E. Aguilar, Gregory C. Fu
Summary: This study reports an iron catalyst for cross-coupling reactions of alkyl electrophiles using olefins and hydrosilanes instead of alkylmetal reagents. Carbon-carbon bond formation occurs at room temperature, and the method utilizes commercially available components. Mechanistic studies suggest the generation of an alkyl radical from the alkyl electrophile and reversible elementary steps.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Engineering, Environmental
Tehseen Nawaz, Muhammad Ahmad, Mohd Zahid Ansari, Iftikhar Hussain, Xi Chen, Li-Juan Liu, Rajat Walia, Kam Hung Low, Shengli Zhuang, Kaili Zhang, Jian He
Summary: Fast-charging storage devices have gained attention for their potential applications in microelectronic gadgets and hybrid electric vehicles. The use of atomically precise metal nanoclusters (NCs) in supercapacitors is rare, but the synthesis of structurally distorted doped Au38_xAgx NCs protected by 2,4-dimethylbenzenethiolate (2,4-DMBT) and their integration with ZIF-8 (Au38_xAgx NCs@ZIF-8) have been studied for electrochemical and physicochemical research. The enhanced electronic transfer kinetics and improved specific capacitance make the doped Au38_xAgx NCs@ZIF-8 based hybrid supercapacitor (HSC) a promising option for next-generation energy storage devices.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Zhuo-Yan Wang, Dylan J. Freas, Gregory C. Fu
Summary: In this paper, a mild method for the synthesis of carbon-fluorine bonds by fluorination of hindered alkyl halides was reported. The method is simple and compatible with various functional groups.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Shengli Zhuang, Dong Chen, Wai-Pan Ng, Dongyi Liu, Meng-Ying Sun, Xia Wu, Yao Zhang, Zekun Li, Yong-Liang Huang, Jun Yang, Jun Yang, Jian He
Summary: This study successfully synthesized a phosphinous acid-phosphinito gold nanocluster with a tetra-icosahedral kernel using a mixed-ligand strategy, and found that phosphinous acid-phosphinito ligands exhibit excellent catalytic activity in electrocatalytic reactions.
Article
Chemistry, Multidisciplinary
Shengli Zhuang, Dong Chen, Wai-Pan Ng, Dongyi Liu, Li-Juan Liu, Meng-Ying Sun, Tehseen Nawaz, Xia Wu, Yao Zhang, Zekun Li, Yong-Liang Huang, Jun Yang, Jun Yang, Jian He
Summary: In this study, a gold nanocluster with a tetra-icosahedral kernel was successfully synthesized using a mixed-ligand strategy. It was found to exhibit high stability and excellent electrocatalytic performance in the oxygen reduction reaction.