Article
Chemistry, Organic
Jian-Fei Bai, Jianbo Tang, Xiaolong Gao, Zhi-Jiang Jiang, Bencan Tang, Jia Chen, Zhanghua Gao
Summary: We report an acid-catalyzed formal cycloaddition and dehydrative substitution reaction of tertiary propargylic alcohols and heteroareneboronic acids. The regioselectivity of the reaction is determined by the properties of the substituents on the alkynyl moiety, allowing for the selective construction of fused hetero-cycles, tetrasubstituted allenes, or 1,3-dienes. This transition-metal-free protocol exhibits high efficiency with a wide range of substrates in up to 89% yield.
Article
Chemistry, Organic
Xiaoshen Ma, Charles S. Yeung
Summary: Our study focused on achieving C(sp(2))-C(sp(3)) coupling reactions using 2,2-difluorobicyclo[1.1.1]pentane (BCP-F-2) building blocks. Through comparison of reactivities between BCP and BCP-F-2 analogues, we found that the Barluenga coupling reaction showed promising results, expanding the potential applications of BCP-F-2 in organic chemistry and medicinal chemistry.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Sara Payamifar, Foad Kazemi, Babak Kaboudin
Summary: This study introduced a convenient nickel-catalyzed protocol for the Suzuki-Miyaura coupling reaction using a simple mixture of Ni(II) and unfunctionalized beta-cyclodextrin in water. The environmentally friendly and cost-efficient method allows the synthesis of biaryls from arylboronic acids and various aryl halides. The catalyst can be recycled for multiple runs with only a small decrease in catalytic activity.
APPLIED ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Kento Asai, Masahiro Miura, Koji Hirano
Summary: A palladium-catalyzed cross-coupling reaction between diarylmethanol derivatives and diborylmethane has been developed, delivering the corresponding homobenzylic boronates in good yields.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Yanhui Wang, Xiaotian Qi, Qiao Ma, Peng Liu, Gavin Chit Tsui
Summary: The diastereoselective synthesis of densely functionalized tetrasubstituted (E)-monofluoroalkenes via Pd(0)-catalyzed base-free Suzuki-Miyaura crosscouplings offers a significant method for producing pharmaceutically relevant compounds. Computational studies support the reaction design, revealing an intriguing mechanism of C-F bond activation leading to complete control of stereoselectivity. This method does not require extraneous base assistance, making it a powerful tool for stereocontrolled synthesis of monofluoroalkenes.
Article
Multidisciplinary Sciences
Jiayin Zhang, Xihao Chang, Xianghong Xu, Hongyi Wang, Lingzi Peng, Chang Guo
Summary: This study demonstrates the nickel-catalyzed dienylation and enantioselective allenylation of phosphine oxides, showing high selectivity in terms of chemo-, regio-, and enantioselectivity.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Daichi Ikeshita, Yusuke Masuda, Naoki Ishida, Masahiro Murakami
Summary: A photoinduced hydrophosphination reaction of terminal alkynes with tri(o-tolyl)phosphine to form alkenylphosphonium salts is reported herein. This sustainable reaction eliminates the need for complex starting materials and expensive transition metals. The o-methyl groups of tri(o-tolyl)phosphine serve two important roles in guiding the phosphorus radical addition onto the terminal sp carbon and intramolecular hydrogen atom transfer.
Article
Chemistry, Multidisciplinary
Guangwu Sun, Herui Liu, Xiu Wang, Wenbo Zhang, Wenjun Miao, Qinyu Luo, Bing Gao, Jinbo Hu
Summary: In this manuscript, a novel palladium-catalyzed coupling reaction between gem-difluoroalkenes and aryl boronic acids is reported, which yields bioactive indane-type ketones with an all-carbon alpha-quaternary center. The mechanism involves a water-induced defluorination and cross-coupling cascade pathway, supported by characterization and stoichiometric reactions of the key intermediates RCF2PdII. The use of vinyl difluoromethylene motif as an in situ carbonyl precursor is unprecedented in transition-metal-catalyzed coupling reactions, and it is expected to spark broad interest in ketone synthesis, fluoroalkene functionalization, and design of new synthetic protocols based on the unique reactivity of difluoroalkyl palladium(II) species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Wei Chen, Wanzhi Chen, Miaochang Liu, Huayue Wu
Summary: The palladium-catalyzed Suzuki-Miyaura cross-couplings of nitroarenes and heteroarylboronate esters has been developed, leading to the synthesis of various heterobiaryl compounds. The practicality of this approach is demonstrated through the synthesis of druglike molecules.
Article
Chemistry, Organic
Yan-Yan Guan, Xiao-Xue Wu, Yu-Fang Liu, Jian-Bin Chao, Zhen-Kang Wen
Summary: A palladium-catalyzed desulfurative coupling of allylthioethers with organoboronic acids is described, which shows high chemoselectivity and good functional group tolerance, enabling the synthesis of a wide range of alpha-branched enones under mild reaction conditions. This method also provides a new retrosynthetic disconnection to multifunctionalized allylic molecules via selective cleavage of the C-S bond, serving as a complementary allylation protocol to Tsuji-Trost reactions.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Felipe Verdugo, Ricardo Rodino, Martin Calvelo, Jose Luis Mascarenas, Fernando Lopez
Summary: The reactivity of carbonyl-tethered alkylidenecyclopropanes (ACPs) can be directed towards tandem cycloisomerization/cross-coupling processes by using Pd-0 catalysts with phosphorus-based monodentate ligands. This allows for the synthesis of a wide variety of highly functionalized cyclic alcohols and amines through the formation of key pi-allyl oxapalladacyclic intermediates which are trapped with external nucleophilic partners.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Chau Ming So, On Ying Yuen, Shan Shan Ng, Zicong Chen
Summary: This study presents a general chemoselective Suzuki-Miyaura coupling using a Pd/L33 catalyst, showing efficient coupling of polyhalogenated aryl triflates by controlling reactivity order and key factors, achieving high yields and chemoselectivity with low Pd catalyst loading.
Article
Chemistry, Organic
Jia-Qing Zhuang, Ying-Qiong Guo, Chen-Liang Deng, Xing-Guo Zhang, Hai-Yong Tu
Summary: A practical and efficient method for the synthesis of methylsulfonyl oxazoles was developed using a tetramethylammoniumiodide(TBAI)-mediated cyclization and methylsulfonylation of propargylicamides. This transition metal-free and oxidant-free reaction utilizes dimethyl sulfite as a SO2 surrogate and methyl source, and exhibits good functional group compatibility with moderate to excellent yields.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Dmitry A. A. Dulov, Tatiana V. V. Magdesieva
Summary: It has been demonstrated that inexpensive and readily available N,N'-diaryldihydrophenazines can effectively replace Ir(III)- and Ru(II)-based photocatalysts in the dual photoredox/Ni(II)C-N coupling of aryl halides with a wide range of anilines, as shown by 32 examples. This efficient and operationally simple approach to diarylamines can be scaled up using a flow apparatus.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Jin Zhang, Xin Wang, Jiale Liu, Xiaogang Wang, Xinkan Yang, Qun Zhao, Yangmin Ma, Ran Fang, Michal Szostak
Summary: Here, we report a mild Ru(0)-catalyzed cleavage of C(aryl)-O bonds enabled by a combination of a Ru-3(CO)(12) catalyst and an imine auxiliary. This method offers rapid entry to synthetically valuable biaryl aldehydes from abundant anisoles. The synthetic utility of this strategy has been demonstrated in sequential processes to construct complex biaryls, exploiting the orthogonal selectivity of C-O bond activation.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Guolin Wu, Yuan Yao, Gen Li, Xue Zhang, Hui Qian, Shengming Ma
Summary: This study developed a catalytic recipe of copper halides to address the issues of side reactions and selectivity in the 1,5-H transfer of alka-1,4-diyn-3-yl amines, providing various allenynes with excellent enantioselectivities. The method was successfully applied to the first highly enantioselective total synthesis of the natural product scorodonin. Mechanistic studies and DFT calculations elucidated the regioselectivity for the observed 1,5-H transfer.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Huanan Wang, Hui Qian, Junliang Zhang, Shengming Ma
Summary: In this study, a palladium-catalyzed enantioselective carbon-phosphorus bond formation reaction affording axially chiral allenyl phosphonates has been developed. The reaction shows high enantioselectivity and good compatibility with a wide range of functional groups.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Qi Liu, Jian Zheng, Xue Zhang, Shengming Ma
Summary: In this study, visible light was successfully integrated into a transition metal-catalyzed coupling reaction to selectively form substituted allenenitriles. Mechanistic studies have shown that the reaction proceeds through a visible light-induced redox-neutral reductive quenching radical mechanism.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Chaoyan Ma, Can Li, Jiahui Bai, Junzhe Xiao, Yizhan Zhai, Yinlong Guo, Shengming Ma
Summary: In this study, a rhodium-catalyzed C-H functionalization-based intermolecular allylation of indoles with trisubstituted allenes has been developed. The synthetic process demonstrates excellent regioselectivity, Z-selectivity, high efficiency of chirality transfer, and a wide tolerance of reactive functional groups under mild conditions. Late-stage modification on complex bioactive or drug molecules has been achieved, along with various synthetic transformations. A reaction mechanism has been proposed based on mechanistic experiments and SAESI-MS studies.
Article
Chemistry, Multidisciplinary
Yulin Han, Anni Qin, Qian Zhang, Xue Zhang, Hui Qian, Shengming Ma
Summary: The Rh-catalyzed reaction allows for the efficient synthesis of cis-fused bicyclic products with excellent selectivity and tolerance towards synthetically useful functional groups. The proposed mechanism involves the rapid racemization of the allene moiety in the starting materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Haibo Xu, Shengming Ma
Summary: An efficient method for synthesizing benzazocines through a double allene protocol has been developed. The reaction involves a highly selective palladium-catalyzed formal [6+2] annulation of allenyl benzoxazinanones with terminal allenes, resulting in the formation of challenging 8-membered cycles. The reaction exhibited decent yields, excellent regioselectivity, and remarkable Z-stereoselectivity for the exo-cyclic C=C bonds. The synthetic potential of benzazocine products has been demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Qian Zhang, Jiabin Zhang, Hui Qian, Shengming Ma
Summary: An efficient aerobic oxidation method using Fe(NO3)(3)center dot 9H(2)O and 4-OH-TEMPO as catalysts at room temperature has been developed for isochromans and their derivatives. This method provides a convenient approach for synthesizing biologically active isochromanone-containing compounds. Optically active products can be prepared from optically active isochromans without racemization. This catalytic protocol can also be extended to the oxidation of xanthene and phthalan in satisfactory yields.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Junlin Li, Jinxian Liu, Chunling Fu, Shengming Ma
Summary: In this study, a combination of Fe(NO3)(3)center dot 9H(2)O/TEMPO/KCl catalysts was identified to efficiently catalyze the aerobic oxidation of 1,4-diols to yield gamma-butyrolactones under mild conditions. The reaction showed good chemo- and regioselectivity towards symmetrical and unsymmetrical 1,4-diols. Optically active gamma-lactones could also be obtained without loss of enantiomeric excess (ee) from optically active 1,4-diols using this method. Furthermore, this approach was successfully applied in the synthesis of the commercial drug NBP.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Shan Huang, Kaihang Wang, Stephen L. Mayo
Summary: A recent study shows that CbAgo, a prokaryotic argonaute, can induce DNA interference and generate double-stranded breaks in target DNAs. The study demonstrates that CbAgo can cleave genome target sites and induce chromosome recombination in Escherichia coli. The findings suggest that the guide-directed cleavage of pAgo on the host genome is mutagenic and can be utilized in genetic manipulation.
NUCLEIC ACIDS RESEARCH
(2023)
Article
Multidisciplinary Sciences
Jie Han, Siyuan Liu, Huanan Wang, Jie Wang, Hui Qian, Zhiming Li, Shengming Ma, Junliang Zhang
Summary: The 13-H elimination is a crucial step in the carbon-palladium bond quenching for the Heck reaction and has been a challenge to control enantioselectivity. Here, we developed a concise and efficient method to construct chiral allenes from fully substituted enol triflates through enantioselective 13-H elimination of alkenyl palladium species under mild conditions. The identified Xu-Phos catalysts play a crucial role in chemoselectivity and enantioselectivity. Multiple linear regression analysis shows the significance of steric effect on enantioselectivity. DFT calculations propose an intramolecular base-assisted deprotonation mechanism for this progress, and energy decomposition analysis suggests that the difference in electrostatic energy of the transition states dominates the stereoselectivity.
Article
Chemistry, Multidisciplinary
Weiyi Wang, Dongyu Huang, Yibo Yu, Hui Qian, Shengming Ma
Summary: In this study, a robust chem-stamp strategy was developed for the modular concise synthesis of terpenoids with isoprene unit(s). The strategy involves two steps: one-carbon extension of aldehydes to alkenyl boronates and the rhodium-catalyzed reaction of alkenyl boronates with 2,3-allenols. This approach enables the construction of various natural and pharmaceutically active terpenoids.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Dongjie Zhang, Junjie Fan, Yaqi Shi, Yankai Huang, Chunling Fu, Xiaoyan Wu, Shengming Ma
Summary: Allenenitriles with diverse functional groups were synthesized smoothly from 5-alkynyl fluorosulfonamides under redox neutral conditions, providing good yields and excellent chemo- and regio-selectivity. The resulting allenenitriles can be easily converted into useful functionalized heterocycles. Mechanistic studies confirmed that this represents the first example of radical-based non-activated propargylic C-H functionalization for allene synthesis.
Article
Chemistry, Multidisciplinary
Yibo Yu, Di Zhai, Zhengnan Zhou, Sheng Jiang, Hui Qian, Shengming Ma
Summary: In this article, a copper-catalyzed aerobic oxidation of primary alcohols to carboxylic acids with TEMPO and KHSO4 as co-catalysts is reported. The reaction demonstrates excellent substrate scope and functional group compatibility under mild conditions. Even sensitive chiral alcohols, chiral amino alcohols, and alcohol-containing steroid skeletons can be oxidized to the corresponding carboxylic acids or lactones without racemization.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Jie Wang, Hui Qian, Shengming Ma
Summary: In this contribution, a palladium-catalyzed cross-coupling reaction was developed for the synthesis of conjugated allenynes. The reaction showed excellent efficiency and selectivity, resulting in high yields of diversely substituted allenynes. The synthetic method demonstrated potential utility in gram-scale reactions and synthetic transformations.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Huanan Wang, Hui Qian, Junliang Zhang, Shengming Ma
Summary: A new reaction method for the synthesis of axially chiral allenyl phosphonates through palladium-catalyzed carbon-phosphorus bond formation has been developed. The reaction exhibits high yields and enantioselectivity, and can accommodate a wide range of functional groups. Mechanistic studies have revealed an important kinetic resolution process.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Chemistry, Multidisciplinary
Dan He, Yawen Li, Fuwen Zhao, Yuze Lin
Summary: High trap density in organic solar cells leads to localized charge carriers and reduced carrier lifetime, limiting device efficiency. This feature article summarizes the recent advances of trap suppression by material design and device engineering.
CHEMICAL COMMUNICATIONS
(2024)
Review
Chemistry, Multidisciplinary
Olivier Monfort, Arshitha Madhusudhan, Martin Motola
Summary: This article presents the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation and discusses their synergy. It critically examines the simultaneous triggering of these two processes and provides insights into research approaches. The study aims to enhance understanding of this complex process and highlight the potential integration of new catalysts in current wastewater treatment technology.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Manideepa Dhar, Chittaranjan Mishra, Avijit Das, Uttam Manna
Summary: An approach of 'polymerization of monomers in its aggregated form' has been introduced to tailor the water wettability of fibrous and porous substrates, achieving hydrophobicity to superhydrophobicity transition, as well as patterned wettability. This facile chemical method provides a durable coating with adjustable and patterned wettability for various potential applications.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Saswat Ranjan Bhoi, Chhanda Debnath, Shikha Gandhi
Summary: In this article, a novel catalytic reaction using Pd(0) and Bronsted acid is reported for the synthesis of biologically important imidazolidinone-fused N-heterocycles through redox-neutral intramolecular N-allylation of indoles and pyrroles with alkynes. This atom-economical method is applicable to a wide range of substrates and eliminates the need for leaving groups or oxidizing agents commonly used in traditional allylation reactions.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Alice Kennett, Sven Epple, Gabriella van der Valk, Irene Georgiou, Evelyne Gout, Romain R. Vives, Angela J. Russell
Summary: This study presents the design and synthesis of sulfated disaccharide inhibitors based on IdoA(2S)-GlcNS(6S), which showed potent inhibition of Sulf-2. The results suggest that IdoA(2S)-GlcNS(6S) is the shortest fragment size required for effective inhibition of Sulfs, and a trisulfated disaccharide is identified as the minimal fragment size of heparan sulfate for effective endosulfatase inhibition.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Mauro Garbini, Andrea Brunetti, Riccardo Pedrazzani, Magda Monari, Massimo Marcaccio, Giulio Bertuzzi, Marco Bandini
Summary: The self-adaptability of galvanostatic electrolysis was found to be helpful in a multistage chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. Through a series of reductive events, densely functionalized cyclopentanes with five contiguous stereocenters were obtained (25 examples, yields up to 95%, dr values up to >20:1). Further experimental and electrochemical investigations indicated the crucial role of dynamic kinetic resolution of the aldol intermediate in the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Dhananjay S. Nipate, Neha Meena, Prakash N. Swami, Krishnan Rangan, Anil Kumar
Summary: In this study, the synthesis of functionalized benzo[a]phenazines and indazolo[2,3-a]quinolines was achieved through Rh(III)-catalyzed oxidative annulation of 2-arylquinoxalines and 2-aryl-2H-indazoles with allyl alcohols. The method showed a wide substrate scope, excellent functional group tolerance, good to high yields of annulated products, and the capability for scaled-up synthesis. A tentative mechanism of the annulation reaction was proposed based on a preliminary mechanistic investigation.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan
Summary: A new lead tellurium borate material with a unique fundamental building block [B4O10] was synthesized and found to exhibit high birefringence. The structure-property relationship was discussed using first-principles calculations.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Amresh Kumar Singh, Baishali Thakurta, Anupam Giri, Monalisa Pal
Summary: This study introduces three key concepts for the quick synthesis of large-scale high-quality 2D materials films and their utilization in device fabrication.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Reina Hagiwara, Shun Nishimura, Kosuke Okeyoshi
Summary: A copolymer-conjugated nanocatalytic system has been developed to improve electron transfer and enhance photoinduced H2 generation.
CHEMICAL COMMUNICATIONS
(2024)
