Article
Chemistry, Organic
Xiaoqin Ning, Yongke Chen, Fangdong Hu, Ying Xia
Summary: This study presents the palladium-catalyzed cross-coupling reactions of cyclobutanone-derived N-sulfonylhydrazones with aryl or benzyl halides, demonstrating that the metal carbene process and beta-hydride elimination can occur smoothly in strained ring systems to yield structurally diverse products. The preliminary success in asymmetric carbene coupling reactions in strained ring systems offers a promising route for the synthesis of enantioenriched four-membered-ring molecules.
Review
Chemistry, Organic
Wang Yuchao, Liu Jinbiao, He Zhitao
Summary: This paper summarizes the development, advancements and mechanistic features of palladium-catalyzed asymmetric hydrofunctionalizations of conjugated dienes. Based on the types of allylic stereogenic centers constructed, the review is divided into six parts.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Yiding Wang, Lei Shen, Helin Wang, Yixin Luo, Qingle Zeng
Summary: The ring-opening addition reaction of activated vinyl cyclopropanes with N-tosylhydrazones in the presence of palladium(0) and triphenylphosphine yields N-tosylhydrazone butenylmalonate compounds. Aromatic aldehyde-derived N-tosylhydrazones produce both terminal and internal N-allylated products, with the terminal products being the major ones. On the other hand, ketone-derived tosylhydrazones only yield terminal addition products. The transformation relationship between the terminal and internal N-allylated products is also observed. A reasonable mechanism based on preliminary experimental results is proposed.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Hui-Yi Yang, Liang-Quan Lin, Na-Qi Li, Zhi-Hui Ren, Zheng-Hui Guan
Summary: In this study, we reported a novel palladium-catalyzed selective branched 3,4-hydroaminocarbonylation of 1,3-dienes to synthesize beta,gamma-unsaturated amides. This reaction utilizes readily available starting materials and tolerates a wide range of functional groups, providing an easy and effective approach to access diverse alpha-substituted beta,gamma-unsaturated amides. Mechanistic investigations suggest that the hydropalladation of dienes is irreversible and the insertion of CO into the allyl-Pd species is likely the rate-limiting step.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Organic
Xiaoqin Ning, Yongke Chen, Qian Ye, Fangdong Hu, Ying Xia
Summary: A palladium-catalyzed cross-coupling reaction between cyclobutenone N-tosylhadrazones and organohalides has been developed. The reaction involves the generation of a strained allylpalladium intermediate and subsequent electrocyclic ring opening and β-hydride elimination to produce conjugated enynes and enallenes. The broad substrate scope, high yields, and tunable product diversity make this protocol potentially valuable in organic synthesis.
Article
Chemistry, Multidisciplinary
Wei Sun, Meng-Yang Hu, Zhan-Sheng Lu, Ming-Yao Huang, Xin-Yu Zhang, Shou-Fei Zhu
Summary: This article reports a method for stereoselective transformation using an iron catalyst to synthesize Z-allylsilanes with high regioselectivity and exclusive stereoselectivity from E/Z mixtures. The mechanism of this reaction differs from previously reported mechanisms.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Haixia Zhao, Yuchen Jiang, Tongqing Weng, Yongjia Shang, Jian Wang
Summary: A three component construction of conjugated 1,3-dienes bearing oxindoles or isoquinolinediones from alkenylated aryl iodides, allenes and diazo compounds via a palladium catalyzed sequential alkene/allene/carbenoid insertion reaction was developed. Three C-C bonds were formed in high order, offering access to multi-substituted dienes in high yields and up to > 20:1 E/Z selectivities. The reaction features excellent functional groups tolerance under mild conditions.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Jiajin Zhao, Guoxiong Xu, Xue Wang, Jiren Liu, Xiang Ren, Xin Hong, Zhan Lu
Summary: A cobalt-catalyzed multipositional isomerization of conjugated dienes using an 8-oxazoline iminoquinoline ligand has been reported. This reaction is simple and efficient, yielding disubstituted 1,3-dienes with good yields and stereoselectivity.
Article
Chemistry, Organic
Chang-Xue Gu, Jian-Guo Liu, Wen-Wen Chen, Ming-Hua Xu
Summary: An efficient base-free palladium-catalyzed intramolecular cross dehydrogenative coupling has been developed for the synthesis of diversely substituted coumaronochromones with yields up to 90%.
Article
Chemistry, Multidisciplinary
Hongyu Guo, Sheng Zhang, Yang Li, Xiaoqiang Yu, Xiujuan Feng, Yoshinori Yamamoto, Ming Bao
Summary: A palladium-catalyzed tail-to-tail reductive dimerization reaction of terminal alkynes is reported for the first time, leading to the efficient transformation of aromatic and aliphatic alkynes into 2,3-dibranched butadienes. The control of reaction solution acidity, achieved by a combination of pivalic acid and para-toluenesulfonic acid, is crucial for the selective tail-to-tail reductive dimerization reaction, which is proposed to proceed via a cationic alkenyl palladium intermediate under acidic conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Ziyan Zhang, Vladimir Gevorgyan
Summary: A mild palladium hydride-catalyzed difunctionalization of conjugated dienes and enynes is reported. This method enables the chemoselectivity switch of the initial hydropalladation step by enhancing the hydricity of PdH species with visible light, allowing for cascade annulation of various easily available and abundant substrates, such as acrylic acids, acrylic amides, and Baylis-Hillman adducts, towards a wide range of alkenyl or alkynyl lactones, lactams, and tetrahydrofurans.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Xiaoyan Wu, Junjie Fan, Xin Huang, Shengming Ma
Summary: An unexpected rhodium-catalyzed reaction has been reported for the synthesis of specific compounds with high efficiency, showing great potential for further research and applications.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Multidisciplinary Sciences
Madeleine C. Deem, Joshua S. Derasp, Thomas C. Malig, Kea Legard, Curtis P. Berlinguette, Jason E. Hein
Summary: Ring walking in Buchwald-Hartwig amination reactions is influenced by the chelating nature of the ligand, while the resting state of the catalyst has no impact. The study also differentiates catalysts that undergo ring walking from diffusion-controlled coupling. The insights gained from this study were used to achieve the desymmetrization of a tetrabrominated precursor.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Jie Huang, Ling-Ling Chen, Zhi-Min Chen
Summary: A palladium-catalyzed regioselective 1,2-alkynyl-carbonalization of conjugated dienes with ethynylbenziodazolone (EBZ) and indoles has been developed, providing easy access to various molecules containing alkenyl, alkynyl, and indole groups. The resulting products are also suitable for various derivatizations.
Article
Chemistry, Multidisciplinary
Yaxin Zeng, Hui Yang, Jiayi Du, Qin Huang, Guoliang Huang, Ying Xia
Summary: The control of linear/branched selectivity in transition-metal catalyzed allyl-allyl cross-coupling reactions has been investigated in this study. It has been found that the terminal/internal regioselectivity can be switched by fine-tuning the rhodium catalytic system. Different types of 1,5-dienes are produced with good yields, exhibiting isomerized terminal, internal, and terminal regioselectivity.
Article
Chemistry, Analytical
Roman Picazo-Frutos, Quentin Stern, John W. Blanchard, Olivier Cala, Morgan Ceillier, Samuel F. Cousin, James Eills, Stuart J. Elliott, Sami Jannin, Dmitry Budker
Summary: Zero- to ultralow-field nuclear magnetic resonance is a magnetic resonance experiment that does not require strong superconducting magnets. It allows high-resolution detection of nuclear magnetism through metal and within heterogeneous media. By using dissolution dynamic nuclear polarization, signals in zero-field nuclear magnetic resonance experiments can be enhanced on sample mixtures, and this technique can be applied to a wide range of molecules. The signal enhancements can reach up to 11,000 compared to thermal prepolarization in a 2 T permanent magnet. The relaxation effects of the TEMPOL radicals used in the hyperpolarization process at zero- and ultralow-fields are also investigated to further increase the signal in future experiments.
ANALYTICAL CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
James Eills, Dmitry Budker, Silvia Cavagnero, Eduard Y. Chekmenev, Stuart J. Elliott, Sami Jannin, Anne Lesage, Joerg Matysik, Thomas Meersmann, Thomas Prisner, Jeffrey A. Reimer, Hanming Yang, Igor V. Koptyug
Summary: Magnetic resonance techniques, especially medical magnetic resonance imaging, are widely used in various scientific disciplines and practical applications. The development of spin hyperpolarization has greatly boosted both fundamental and applied magnetic resonance. Hyperpolarization techniques significantly enhance the signal intensity of magnetic resonance, overcoming its low sensitivity and opening up new possibilities for applications.
Article
Chemistry, Organic
Xi Zhao, Xiaofeng Yu, Mingjun Liu, Yanping Huo, Shaomin Ji, Xianwei Li, Qian Chen
Summary: An efficient synthesis of 9-benzylated fluorenols with high atom economy (<= 91% yield) has been achieved through an external photocatalyst-free benzylic C-H functional-ization using fluorenones under visible-light irradiation. Spectroscopic studies suggest that the photoexcited fluorenones undergo a reductive quenching with toluene derivatives to generate ketyl radicals and benzyl radicals, which then undergo a cross-coupling reaction to yield the desired fluorenols.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Bairong Liu, Yabo Chen, Qixin Liang, Yuyao Liang, Bifu Liu, Yuan Liu, Yang Gao, Qian Chen, Yanping Huo, Xianwei Li
Summary: Regiodivergent [3+2] and [4+2] C-H annulation of imines and imidate esters with unsymmetrical alkynes has been achieved under Rh(III) catalysis. Further transformation of the aldehyde and TMS functionality on the indene products is also demonstrated. The current work highlights the alcohols-directed multiple C-H annulation of imines and imidate esters, leading to diverse fused heterocycles.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Physics, Multidisciplinary
Kai Wei, Tian Zhao, Xiujie Fang, Zitong Xu, Chang Liu, Qian Cao, Arne Wickenbrock, Yanhui Hu, Wei Ji, Jiancheng Fang, Dmitry Budker
Summary: Achieving high energy resolution in spin systems is important for fundamental physics research and precision measurements. We found a new relaxation mechanism in alkali-noble-gas comagnetometers and demonstrated a tenfold increase in nuclear spin hyperpolarization and coherence time with optimal hybrid optical pumping. Our proposed use of this comagnetometer can surpass previous limits in searching for exotic spin-dependent interactions.
PHYSICAL REVIEW LETTERS
(2023)
Article
Physics, Multidisciplinary
Rui Zhang, Dimitra Kanta, Arne Wickenbrock, Hong Guo, Dmitry Budker
Summary: We present an alignment-based 87Rb magnetometer that overcomes the issue of nonlinear Zeeman splitting in alkali-metal atomic magnetometry. The magnetometer exhibits immunity to NLZ-related errors due to a single magnetic resonance peak and well-separated hyperfine transition frequencies. Experimental results show that the magnetometer can be used for practical measurements in geomagnetic environments, achieving a photon-shot-noise-limited sensitivity of 9 fT/pat 5 mu T and remaining stable at tens of fT/ ffiffiffiffiffiffiffiffiffiffiHz p at Hz 50 mu T at room temperature.
PHYSICAL REVIEW LETTERS
(2023)
Article
Physics, Multidisciplinary
Xue Zhang, Abhishek Banerjee, Mahapan Leyser, Gilad Perez, Stephan Schiller, Dmitry Budker, Dionysios Antypas
Summary: The effects of scalar and pseudoscalar ultralight bosonic dark matter were investigated using quartz oscillator frequencies and atomic transitions. Linear interactions were constrained for scalar dark matter in the mass range of 1 x 10-17-8.3 x 10-13 eV, and quadratic interactions were constrained for pseudoscalar dark matter in the mass range of 5 x 10-18-4.1 x 10-13 eV. These constraints improve upon previous direct searches and astrophysical observations.
PHYSICAL REVIEW LETTERS
(2023)
Article
Physics, Atomic, Molecular & Chemical
Danila A. Barskiy, John W. Blanchard, Dmitry Budker, Quentin Stern, James Eills, Stuart J. Elliott, Roman Picazo-Frutos, Antoine Garcon, Sami Jannin, Igor V. Koptyug
Summary: The combination of nuclear hyperpolarization technique with (near-)zero-field modalities has great potential in various applications of nuclear magnetic resonance spectroscopy and imaging, such as biomedical diagnostics and monitoring catalytic reactions in metal reactors.
APPLIED MAGNETIC RESONANCE
(2023)
Article
Chemistry, Organic
Yupeng Zhao, Yang Gao, Zhongke Xie, Shuwei Liao, Jiebin Huang, Yanping Huo, Qian Chen, Xianwei Li, Xiao-Qiang Hu
Summary: Different chemoselectivities were observed between phenols and thiophenols in the Tf2O-promoted C3 functionalization of simple anthranils. Phenols and anthranils react to form 3-aryl anthranils via a C-C bond formation, while thiophenols form 3-thio anthranils through a C-S bond formation. Both reactions have a broad substrate scope and tolerate a wide range of functional groups, yielding the corresponding products with specific chemoselectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Quantum Science & Technology
Jabir Chathanathil, Dmitry Budker, Svetlana A. Malinovskaya
Summary: A chirped-pulse quantum control scheme called C-CARS is proposed for enhancing the vibrational coherence in molecules during coherent anti-Stokes Raman scattering spectroscopy. The scheme involves chirping of the pump, Stokes, and probe pulses in the four-wave mixing process of CARS to satisfy the conditions of adiabatic passage. By utilizing the rotating wave approximation and adiabatic elimination of excited state manifold, the four-level model system is simplified into a "super-effective" two-level system. It is demonstrated that the excitation selectivity of vibrational degrees of freedom can be controlled by adjusting the spectral chirp rate of the pulses. The robustness, spectral selectivity, and adiabatic nature of this method make it advantageous for improving CARS spectroscopy for sensing, imaging, and detection purposes.
QUANTUM SCIENCE AND TECHNOLOGY
(2023)
Article
Optics
Derek F. Jackson Kimball, Dmitry Budker, Timothy E. Chupp, Andrew A. Geraci, Shimon Kolkowitz, Jaideep T. Singh, Alexander O. Sushkov
Summary: This article surveys the applications of spin-based quantum sensors in measurements probing fundamental physics. Experimental methods and technologies developed for spin-based quantum information science have rapidly advanced, enabling precise control and measurement of spin dynamics. Theories beyond the standard model predict phenomena such as discrete-symmetry-violating electromagnetic moments correlated with particle spins, exotic spin-dependent forces, and coupling of spins to ultralight bosonic dark-matter fields. Spin-based quantum sensors provide a methodology complementary to particle colliders and large-scale particle detectors, offering a way to search for these phenomena and test fundamental physics. The article also highlights areas of technological development that can enhance the sensitivity of spin-based quantum sensors to new physics.
Article
Chemistry, Multidisciplinary
James Eills, Roman Picazo-Frutos, Dudari B. B. Burueva, Larisa M. M. Kovtunova, Marc Azagra, Irene Marco-Rius, Dmitry Budker, Igor V. V. Koptyug
Summary: We demonstrate a catalyst-free approach to produce hyperpolarized [1-C-13]succinate in aqueous solutions, utilizing parahydrogen-induced polarization (PHIP) and a combination of homogeneous and heterogeneous catalytic hydrogenation reactions. A homogeneous ruthenium catalyst and para-enriched hydrogen gas are employed for PHIP to generate hyperpolarized [1-C-13]fumarate, followed by the removal of the toxic catalyst and reaction side products through a purification procedure. A second hydrogenation reaction is carried out using normal hydrogen gas and a solid Pd/Al2O3 catalyst to convert fumarate to succinate. This cost-effective method has a turnover time of a few minutes and represents a significant breakthrough for in vivo applications of hyperpolarized [1-C-13]succinate as a contrast agent.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Yuanting Huang, Jinyu Tang, Xi Zhao, Yanping Huo, Yang Gao, Xianwei Li, Qian Chen
Summary: The development of P(O)-heteroatom bond-forming reactions is crucial, but previous methods have limitations. This study presents an efficient and green photocatalytic phosphorylation of heteroatom nucleophiles utilizing acid red 51 as the photocatalyst and air as the oxidant under blue LED irradiation. The reaction exhibits broad substrate scope and provides practical access to phosphinic fluorides, phosphinic amides, phosphoramidates, and phosphinates. Mechanistic studies suggest the involvement of a phosphorus-centered radical cation generated by photocatalytic single electron transfer (SET).
Article
Astronomy & Astrophysics
I. M. Bloch, D. Budker, V. V. Flambaum, I. B. Samsonov, A. O. Sushkov, O. Tretiak
Summary: Scalar-field dark matter models suggest small oscillations of fundamental constants, which could lead to observable variations in the magnetic field of a permanent magnet. We propose an experiment using a SQUID magnetometer or a low-noise radiofrequency amplifier to detect this type of dark matter. Our results show that this experiment may have comparable sensitivity to leading experiments searching for variations of fundamental constants in a frequency range from a few Hz to about 1 MHz. We also discuss the applicability of using variations of fundamental constants to account for the interaction with scalar dark matter.
Article
Chemistry, Organic
Bairong Liu, Jianhang Rao, Weibing Liu, Yang Gao, Yanping Huo, Qian Chen, Xianwei Li
Summary: By tuning the divergent oxidative Heck reaction with O-2 enabled by self-assembled imines, olefins achieved site selectivity and stereoselectivity. The compatibility of strongly coordinating pyridines and quinolines facilitated the concise delivery of selective serotonin 4 receptor ligand, topotecan, and irinotecan analogues.
ORGANIC CHEMISTRY FRONTIERS
(2023)
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)
