Article
Chemistry, Multidisciplinary
Michael W. Milbauer, Jeff W. Kampf, Melanie S. Sanford
Summary: In this study, we successfully isolated a cyclometalated nickel(IV) complex that is similar to a key intermediate proposed in aminoquinoline-directed C-H functionalization catalysis. The complex undergoes bond-forming reaction under mild conditions and demonstrates the importance of LX-type ligands in stabilizing these nickel(IV) species.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Qian-Yu Li, Shiyan Cheng, Ziqi Ye, Tao Huang, Fuxing Yang, Yu-Mei Lin, Lei Gong
Summary: This study developed a simplified photochemical system using iron(III) halides as multifunctional reagents and air as a green oxidant to achieve the direct and selective coupling of benzenes with aliphatic hydrocarbons. The method showed high yields and commendable chemo-, site-selectivity, and demonstrated the potential of iron halides in sustainable synthesis.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Xiao-Wen Wang, Rui-Xue Li, Yang Deng, Ming-Qiu-Hao Fu, Ya-Nan Zhao, Zhi Guan, Yan-Hong He
Summary: This article proposes a new method for the direct hydroxylarylation of unactivated benzylic carbons (sp3/sp2/sp) without the need for pre-functionalized benzylic alcohols, aromatic aldehydes, or ketones. It features direct functionalization of unactivated benzylic C(sp3)-H bonds and benzylic sp2/sp-carbons, mild conditions (open air, room temperature), an environmentally friendly procedure (without any external catalyst/mediator/additive), and direct access to sterically hindered alcohols from inexpensive and readily available alkyl/alkenyl/alkynylbenzenes. Mechanistic studies strongly support the proposed radical-radical cross-coupling between transient ketyl radicals and persistent radical anions. Gram-scale synthesis and diversification of drug derivatives demonstrate the practical potential of this protocol.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Zhuang Wang, Kaikai Niu, Yuxiu Liu, Hongjian Song, Qingmin Wang
Summary: A mild and convenient protocol for the synthesis of alpha-alkoxy isochroman derivatives has been reported in this study. The electrochemical alpha-C(sp(3))-H/O-H cross-coupling reactions of isochromans and alcohols in the presence of benzoic acid were used, which facilitated the electro-oxidation process and increased the product yield. The desired coupling products were obtained in moderate to high yields.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Chao Li, Ran Ding, Heng-Yi Guo, Shuang Xia, Lei Shu, Pei-Long Wang, Hongji Li
Summary: In this study, we report a rare catalyst-free electrochemical cross-coupling reaction that can forge various types of chemical bonds at room temperature. The study also reveals the dual role of organotrifluoroborates as both coupling partner and electrolyte in the C-H functionalization reaction.
Article
Chemistry, Multidisciplinary
Weonjeong Kim, Jangwoo Koo, Hong Geun Lee
Summary: A unique functionalization strategy for a benzylic C(sp(3))-H bond has been developed based on the facile oxidation event of indole substrates. The method utilizes mild conditions and exhibits a wide substrate scope for both substituted indoles and C(sp(2))-based reaction counterparts. Competitive hydrogen atom transfer processes, commonly seen in conventional methods, are not involved in the product formation process of this developed strategy.
Article
Chemistry, Organic
Yangyang Wang, Xiaobo Xu, Binghan Pang, Liqiang Hao, Gaorong Wu, Yafei Ji
Summary: In this study, the palladium-catalyzed sequential C(sp(3))-H and C(sp(2))-H bond diolefination reaction of o-toluidine was achieved using acetyl-protected aminoethyl phenyl thioether ligands. This novel reaction allows for the preparation of conjugated diene structure via an immediate second olefination, based on the first C(sp(3))-H olefination, in one pot. Various triflyl-protected anilines and acrylates were elegantly used as coupling partners. Furthermore, the unpurified diolefination products can be easily converted to tetrahydroquinoline derivatives.
Article
Chemistry, Organic
Xinpeng Xie, Kaikai Qiao, Bing-ru Shao, Wenfeng Jiang, Lei Shi
Summary: Cross-dehydrogenative coupling is a powerful tool for constructing C-C and C-heteroatom bonds. In this study, a visible-light-mediated radical CDC of C(sp(3))-H/C(sp(3))-H and C(sp(3))-H/C(sp(2))-H was reported, guided by a phenyl radical and intermolecular hydrogen atom transfer process. This strategy enables the efficient coupling of inert C(sp(3))-H and C(sp(2))-H with alpha-N C(sp(3))-H of amines, showing good regioselectivities and yields. Mechanistic studies revealed that the EDA complex triggers an intermolecular HAT process.
Article
Multidisciplinary Sciences
Shao-Bai Yan, Rui Wang, Zha-Gen Li, An-Na Li, Chuanyong Wang, Wei-Liang Duan
Summary: This paper reports a Cu-catalyzed asymmetric C(sp(2))-H arylation using diaryliodonium salts, which enables the synthesis of a range of chiral phosphonic diamides and chiral phosphine oxide indoles with high selectivity under mild conditions.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Yue Xia, Nicholas W. Wade, Philip N. Palermo, Yidong Wang, Yi-Ming Wang
Summary: This study presents a novel method using iron catalysis to convert simple monosubstituted allenes into 1-tetrahydroisoquinolinyl 1,1-disubstituted allenes, marking a significant advance in chemical synthesis. The optimized protocol shows a wide scope and mild, functional group tolerant conditions.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Jiayuan Wang, Youwan Ye, Tongzhi Sang, Chenxing Zhou, Xiazhen Bao, Yong Yuan, Congde Huo
Summary: A general C(sp3)-H/C(sp3)-H dehydrogenative coupling strategy for the preparation of various natural or unnatural amino acids from readily available glycine derivatives and hydrocarbons is reported, which involves a combination of SET and HAT process.
Article
Chemistry, Organic
Sheng-Yun Zhou, Ding Zhang, Xiao-Jie Liu, Jing-Hao Qin, Zheng-Li Fu, Shuang-Long Li, Fang-Jun Cai, Yang Li, Jin-Heng Li
Summary: A novel photoredox-catalyzed C(sp(3))-C(sp(3)) cross-coupling reaction between N-arylamines and cycloketone oxime esters has been achieved under mild conditions. The redox-neutral reaction shows good functional group tolerance and excellent regioselectivity without the need for additional base or ligand control. Furthermore, this approach has been successfully applied for the late-stage modification of short peptides and analogues.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Jacob R. Ludwig, Eric M. Simmons, Steven R. Wisniewski, Paul J. Chirik
Summary: A cobalt-catalyzed method for the C(sp(2))-C(sp(3)) Suzuki-Miyaura cross coupling of aryl boronic esters and alkyl bromides was developed, with cobalt-ligand combinations being assessed through high-throughput experimentation. The use of cobalt(II) sources with trans-N,N'-dimethylcyclohexane-1,2-diamine (DMCyDA, L-1) resulted in optimal yield and selectivity. The transformation allowed for diverse steric and electronic properties on the aryl boronate nucleophile as well as various levels of branching and synthetically valuable functionality on the electrophile, with radical trap experiments supporting the formation of electrophile-derived radicals during catalysis.
Article
Chemistry, Organic
Fang Wang, Jiaming Chen, Xiaoqi Jia, Dailin Zhuang, Zhenyang Wan, Lifang Ma, Ziyuan Li
Summary: A remote directing group-enabled radical relay strategy for benzylic direct C(sp3)-H alkoxylation with alcohols at room temperature is developed, which achieves satisfactory site-selectivity, chemoselectivity, and reaction scope under simple and mild conditions without the need for ligands or additives.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Canlin Zou, Hongting Wu, Jiangtao He, Yunfei Hu, Weijie Deng, Xinling Li, Jinhui Hu, Yibiao Li, Yubing Huang
Summary: An efficient anodic C(sp(3))-H acyloxylation protocol has been developed, which enables the direct oxidation of indolin-3-ones to obtain various C2-acyloxy indolin-3-ones without the need for metal catalysts and external oxidants. The practicality of this protocol has been demonstrated through the effective application of several medical drugs and gram-scale experiments.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Jindian Duan, Pui Ying Choy, Kin Boon Gan, Fuk Yee Kwong
Summary: A general protocol for N-difluoromethylation of aniline derivatives using commercially available ethyl bromodifluoroacetate as a difluorocarbene source is developed, which exhibits notable operational simplicity, wide functional group tolerance, and good-to-excellent product yields.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Review
Chemistry, Organic
Yi Ling Tsang, Pui Ying Choy, Man Pan Leung, Xinwei He, Fuk Yee Kwong
Summary: Rhodium-catalysed cross-dehydrogenative coupling (CDC) has attracted considerable attention as an attractive synthetic tool for selective C-C bond formation. This process eliminates the need for pre-functionalised starting materials and generates minimal metallic waste, making it more environmentally friendly and sustainable. Moreover, it offers a straightforward synthetic approach using simple materials, resulting in better step- and atom economy.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Inorganic & Nuclear
Ka Yee Yee, Man Pan Leung, Man Ho Tse, Pui Ying Choy, Fuk Yee Kwong
Summary: This paper presents the first general examples of palladium-catalyzed direct C-H olefination of polyfluoroarenes using alkenyl tosylates as electrophilic coupling partners. Good-to-excellent yields of olefinated polyfluoroarenes can be obtained by employing the Pd/L1 catalyst system. The reaction exhibits good structural and functional compatibility, and particularly smooth reactivity for steric demanding and heterocyclic alkenyl tosylates. It can be practically performed on a gram-scale without significant loss of product yields.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Kin Boon Gan, Rong-Lin Zhong, Zhen-Wei Zhang, Fuk Yee Kwong
Summary: In this study, a rational design of a new collection of chiral phosphines featuring a C-N axial chirality is presented. These phosphines were successfully applied in the enantioselective synthesis of highly steric hindered tetra-ortho-substituted biaryls. It was found that the carbazolyl framework played a crucial role in facilitating the reaction through a fleeting Pd-N/Pd-pi coordination.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Qingjing Yang, Zihao Wang, Catherine Hong Huan Hor, Haitao Xiao, Zhaoxiang Bian, Jun (Joelle) Wang
Summary: This study reports a highly efficient kinetic resolution method for the synthesis of chiral flavanols with two stereocenters. In vitro experiments and RNA sequencing analysis revealed the potential anti-inflammation effects of these flavanols.
Article
Chemistry, Organic
Tianyi Liu, Kin Boon Gan, Rong-Lin Zhong, Xinwei He, Fuk Yee Kwong
Summary: This study reports a redox-neutral benzylic C-O cyclization under transition-metal-free conditions utilizing the Tf anion as the leaving group. The protocol delivers a series of captivating helical compounds with various functionality in good-to-excellent yields. It is particularly notable that sterically hindered helical compounds are conformationally stable. In addition, bihelical multiple-ring systems potentially useful in material chemistry can also be easily obtained using this method.
Review
Chemistry, Multidisciplinary
Man Ho Tse, Pui Ying Choy, Fuk Yee Kwong
Summary: This article presents a promising collection of phosphine ligands and explores their applications in modern arylation processes. Using a readily accessible 2-arylindole scaffold, three major phosphino-moiety-positioned ligand series can be generated. The study shows that the balance of steric and electronic properties of phosphine ligands is crucial for the success of the reaction.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Review
Chemistry, Multidisciplinary
Pui Ying Choy, Kin Boon Gan, Fuk Yee Kwong
Summary: Sonogashira cross-coupling protocol allows the construction of C(sp(2))-C(sp) bond through the reaction between aryl/vinyl halide and terminal alkyne. The resulting internal alkynes are versatile for the synthesis of various functionalized alkyne-containing scaffolds or as valuable synthetic synthons. The reaction conditions can be adjusted to activate hindered and/or electron-rich electrophiles, and Pd-catalyzed copper-free Sonogashira coupling reaction has gained attention for being more environmentally friendly and allowing convergent synthesis in a one-pot manner.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Pui Ying Choy, Man Ho Tse, Fuk Yee Kwong
Summary: Transition metal-catalyzed borylation is a powerful strategy for synthesizing organoboron compounds, and it finds widespread applications in various fields. This review provides a concise summary of recent advances in palladium- and rhodium-catalyzed borylation, highlighting catalyst systems, substrates scope, and reaction conditions. The discussion also includes the diverse array of borylative products obtained and future directions for more efficient and selective methodologies.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Qingjing Yang, Jian Zhou, Jun (Joelle) Wang
Summary: An enantioselective hydrophosphination reaction of alkenyl isoquinolines is achieved using a copper-chiral diphosphine ligand catalyst. This method provides a straightforward and efficient synthesis of chiral phosphines containing an isoquinoline moiety, with high yields and excellent enantioselectivities. Additionally, these chiral phosphine products can serve as useful bidentate P,N-ligands with potential applications in asymmetric catalysis.
Article
Chemistry, Organic
Yanan Liu, Pui Ying Choy, Demao Wang, Mengdi Wu, Qiang Tang, Xinwei He, Yongjia Shang, Fuk Yee Kwong
Summary: A 1,8-diazabicyclo[5.4.0]-undec-7-ene-promoted cascade double-annulation of ortho-alkynyl quinone methide is developed for constructing of 2-aryl-4-hydroxybenzo-[c]-chromen-6-ones. This method offers operational simplicity and good functional group compatibility.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Xinwei He, Ruxue Li, Pui Ying Choy, Jiahui Duan, Zhenzhen Yin, Keke Xu, Qiang Tang, Rong-Lin Zhong, Yongjia Shang, Fuk Yee Kwong
Summary: An operationally simple and environmentally friendly method for the modular and regioselective synthesis of (E)-4-(vinyl or aryl or alkynyl)iminochromenes from propargylamines and S-methylated beta-ketothioamides using FeCl3 in undried acetonitrile and air atmosphere is reported. This method exhibits a broad substrate scope and nice functional group compatibility, providing an efficient access to 3,4-disubstituted iminochromenes.
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)
